Electrophotographic material for color proofing

ABSTRACT

An electrophotographic material for color proofing which comprises a substrate, a photoconductive layer and a transfer layer in this order, wherein said photoconductive layer comprises a polymer (P) which contains at least one polymer segment (X) containing not less than 50% by weight of units having fluorine atom(s) and/or silicon atom(s) and at least one polymer segment (Y) containing units having photosetting and/or thermosetting group(s); a polymer (Q) which contains not less than 30% by weight of units represented by the formula (I): 
     
         --CH(b.sup.1)--C(b.sup.2)(COOR.sup.3)-- 
    
     wherein b 1  and b 2  each represents independently a hydrogen atom, and R 3  represents a hydrocarbon group, and contains at least one one-functional macromonomer containing one or more units having polar group such as --PO 3  H 2 , --SO 3  H, --COOH and a residue of a cyclic anhydride in its main chain and a group having polymerizable double bond, 
     the polymer (P) is present at least in the region near the surface facing said transfer layer, and 
     the surface of said photoconductive layer which contacts with the transfer layer has tack strength of not more than 150 gram.force.

BACKGROUND OF THE INVENTION

The present invention relates to an electrophotographic material forcolor proofing, in particular an improvement in a photoconductive layerof the electrophotographic material for color proofing (hereinafter,sometimes referred to as a light-sensitive material).

PS plates have dominantly been used for multicolor printing because oftheir excellence in quality, printing durability, dimensional stabilityand resistance to contamination. PS plates are formed by applying aphotosensitive layer containing a diazo resin or o-quinone diazide as amain component onto an aluminum substrate whose surface has been treatedto improve hydrophilic property thereof. The PS plates are exposed to UVrays through a color-separated and half tone film, developed to removethe photosensitive layer in non-image areas to reveal the surface of thehydrophilic aluminium plate, whereby, printing plates are obtained. Amulticolor image can be obtained by mounting each printing plateprepared by the above process for each color on a printing machine andprinting using an ink corresponding to each color on a sheet of sameprinting paper.

After it is confirmed that a series of processes of editing, platemaking and printing such as input of characters, layout, colordesignation, etc., are conducted as designated, and that there is nodifference between color tone reproduction, etc. obtained and onedesignated by an orderer, necessary corrections are made and then, anext step or regular printing is conducted. This step is called presscorrection. The former is called "first proof", and it is conducted forthe purpose of checking each process in a printing company as mentionedabove. The latter is called "second proof", and it is conducted toobtain an acceptance by the orderer. The second proof is conducted inalmost the same manner as one for regular printing, including the kindof inks and printing paper to be used. The resultant proof has almostthe same quality as one of printed matter obtained in regular printing.Proof printing using regular printing paper to be used in regularprinting is called "regular correction".

Color designation and tone reproduction of a color photograph should beconfirmed and corrected for each color. Especially, the proof for theorderer is generally conducted several times repeatedly. Heretofore,proof printing has been conducted using a color separated and half tonefilm to be used in regular printing, and a PS plate which is relativelylow in cost and printing durability, for example, with the proof press,whose mechanism is similar to a press machine, of the name of "the flatbed four color proof press" made by DAINIPPON SCREEN Co., Ltd. Themethod mentioned above is called "press proof", which is not convenient,since it takes much time to prepare, and requires skill for operation,and is difficult to keep quality constant.

There have been proposed some methods for color proofing which do notuse the proof press having a mechanism similar to one of a pressmachine, and therefore are easier to conduct and stable in printing.They are preferably used because of the advantages such as easieroperation and stability after being used repeatedly. It is called "offpress proof", and typical manners and systems thereof are disclosed inBulletin of the Printing Society of Japan 24, No.3, page 32 (1989).Examples of the systems include systems available in the trade names of"COLOR ART" by Fuji Photo Film Co.,Ltd., "CROMALIN" by Dupont, and"MATCHPRINT" by 3M. The systems use a color separated film, but do notuse the proof press mentioned above.

The color separated film is generally prepared using a color scanner.The scanner reads data from original, and conducts color separation,formation of half tone, and tone reproduction control to output degitaldata. A silver halide film is scan-exposed with laser beams modulated bythe degital data, developed, fixed and dried to obtain a positive ornegative color separated film for multi color printing.

Recently, an electronic plate making system called "total color scanner"has been developed and been utilized. The system conducts procedures upto retouching or plate collecting therein and therefore the systemrequires first proof capable of examining a resultant quality, morerapidly than that heretofore in use. If resultant qualities such as amanner, a layout, quality of color separation for some patterns, tonereproduction are judged with a :ress correction method heretofore inuse, efficiency of the system will be seriously lowered, since it takesa long time for output to color separation film and the preparation ofpress proof or off press proof as prior art proofing.

Since an image data in the system is available as a degital information,some degital direct color proof systems which do not use proofingheretofore in use have been proposed. Details thereof are described in"Printing Information", April, page 2 et seq.(1991). Examples of suchsystems include a silver halide system, an electrostatic toner system (awet electrophotographic system), an ink-jet system and a thermalsublimation transfer system.

Among them, the wet electrophotographic system is especially excellentin precision, image quality and tone reproduction and advantageous forthe reason that any type of paper can be used for the system so thatregular paper correction can be conducted, since, in the system, aphotoconductive element is charged, exposed to laser beam and developedwith every color toner comprising a pigment having four colors, i.e.cyan, magenta, yellow and black dispersed in an electrical insulatingliquid, and then, the resulting toner image is transferred.

However, it is quite difficult to transfer a toner image from thesurface of the photosensitive plate directly to regular paper. JapanesePatent laid open application (hereinafter referred to as "J. P. KOKAI")No. Hei 2-272469 discloses a technique which has solved such problems,but includes several steps.

There have been proposed to provide a releasable transfer layer on thesurface of the photosensitive element, to form a toner image on thetransfer layer and to transfer the image together with the transferlayer to regular paper in J. P. KOKAI Nos. Sho 61-174557 (JapanesePatent publication Hei 2-43185), Hei 1-112264, Hei 1-281464, and Hei3-11347. Among them, the system disclosed in J. P. KOKAI No. Sho61-174557 is only practically used. However, in the system,photoconductive layer is exposed to light through a transparentsubstrate (a polyethylene terephthalate film), and therefore, the systemrequires that the photoconductive layer is also transparent. Inaddition, it is not reusable, Therefore, the system is expensive.

J. P. KOKAI Nos. Hei 1-112264 and Hei 1-281464 disclose an image formingmethod or a color printing method which uses a photosensitive papercomprising a photosensitive element on which a releasable layer and anadhesive layer are applied in order, and which is characterized in thata toner image is developed and transferred to regular paper with thereleasable layer.

However, it is difficult to form such a photosensitive layer uniformlywith a practical size and it is also difficult to transfer a toner imagewithout damage.

The same will apply to the method disclosed in J. P. KOKAI No. Hei3-11347 which uses a recording medium wherein a releasable overcoatinglayer is applied onto a photoconductive layer.

In addition to the problem of reduced quality of the image due to defectof transfer of the toner image as explained above, the problem ofreduced quality of the image due to defect occuring while a toner imageis electrophotographically formed, especially, due to lowering ofelectrostatic properties is desired to be solved.

We have studied properties of electrophotographic materials comprising aknown photoconductive layer under various environmental condition forimaging (e.g. higher or lower temperature, or higher or lower humidity),and have found that electrophotographic properties of the materials(especially dark charge retention property and photosensitivity) werelowered, and the materials could not provide stable and good images insome cases.

When electrophotographic materials for color proofing which can copewith a degital direct system are exposured with semiconductor laserbeams by a scanning exposure method, they are required to have higherelectrophotographic properties such as electrostatic properties,especially dark charge retention property and photosensitivity, sincelonger exposure time is necessary and exposure intensity is limited insuch a process in compared with a conventional overall simultaneousexposure system using visible lights.

When the above mentioned known electrophotographic materials which isknown were used in such a system, quality of resultant images werelowered. Namely, in the resultant images, background contaminationoccured, fine lines disappeared, and batter of characters occured.

SUMMARY OF THE INVENTION

An object of the present invention is to provide an electrophotographicmaterial for color proofing wherein the problem mentioned above issolved.

Another object of the present invention is to provide a proof withoutcolor drift and with excellent precision and image quality easily andconstantly.

A further object of the present invention is to provide aphotoconductive layer which is easily prepared with low cost and hasstable electrophotographic properties.

A still further object of the present invention is to provide a methodfor preparing a color proofing wherein a toner image is easilytransferred with a simple transfer apparatus, and a proof can beprepared on any type of transfer paper.

A still further object of the present invention is to provide anelectrophotographic material for color proofing which can provide clearand good images even if imaging is conducted in unusual environment suchas higher or lower temperature, or higher or lower humidity.

A still further object of the present invention is to provide anelectrophotographic material for color proofing which can provide acolor proof having stable and excellent quality of images irrespectiveof kinds of sensitizing dyes used in the photoconductive layer, and canprovide excellent electrostatic properties even when it is scan-exposedusing semiconductor laser beams.

The problems mentioned above are solved by using an electrophotographicmaterial for color proofing which comprises a substrate, aphotoconductive layer and a transfer layer in this order, and is usedfor preparing a color proof in a process wherein at least one colortoner image is electrophotographically formed on the transfer layer andthen transferred together with said transfer layer to a sheet materialto prepare the color proof, wherein said photoconductive layer comprisesa polymer (P) selected from the group consisting of the followingpolymers (P₁), (P₂), (P₃) and (P₄); a polymer (Q) selected from thegroup consisting of the following polymers (Q₁) and (Q₂); and a polymer(R) containing at least one unit having photo and/or thermosettinggroup(s),

the polymer (P) is present at least in the region near the surfacefacing said transfer layer, and

the surface of said photoconductive layer which contacts with thetransfer layer has tack strength of not more than 150 gram. force, whichis measured by Pressure Sensitive Tape and Sheet Test of JIS Z0237-1980,

the polymer (P₁):

a linear block copolymer which contains at least one polymer segment (X)containing not less than 50% by weight of units having fluorine atom(s)and/or silicon atom(s) and at least one polymer segment (Y) containingunits having photosetting and/or thermosetting group(s);

the polymer (P₂):

a star type copolymer which contains at least three AB type blockcopolymer chains consisting of a polymer segment (X) containing not lessthan 50% by weight of units having fluorine atom(s) and/or siliconatom(s) and a polymer segment (Y) containing units having photosettingand/or thermosetting group(s), and said block copolymer chains arebonded through an organic group (Z);

the polymer (P₃):

a graft copolymer which contains at least one polymer segment (X)containing not less than 50% by weight of units having fluorine atom(s)and/or silicon atom(s) and at least one polymer segment (Y) containingunits having photosetting and/or thermosetting group(s);

the polymer (P₄):

an AB type or ABA type block copolymer which contains at least onepolymer segment (X) containing not less than 50% by weight of unitshaving fluorine atom(s) and/or silicon atom(s) and at least one polymersegment (Y) containing units having photosetting and/or thermosettinggroup(s), wherein at least one said polymer segment (X) is the followinggraft type polymer segment (X'), at least one said polymer segment (Y)is the following graft type polymer segment (Y'), or at least one saidpolymer segment (X) is the following graft type polymer segment (X') andat least one said polymer segment (Y) is the following graft typepolymer segment (Y'):

the graft type polymer segment (X'): a polymer segment which has aweight-average molecular weight of 1×10³ ˜2×10⁴, and contains at leastone macromonomer segment (M_(A)) which contains not less than 50% byweight of units having fluorine atom(s) and/or silicon atom(s);

the graft type polymer segment (Y'): a polymer segment which has aweight-average molecular weight of 1×10³ ˜2×10⁴, and contains at leastone macromonomer segment (M_(B)) which does not contain units havingfluorine atom(s) and/or silicon atom(s);

the polymer (Q₁):

a graft type copolymer having a weight-average molecular weight of 1×10³˜2×10⁴ which is obtained by polymerizing at least one monomerrepresented by the formula (I): ##STR1## wherein b¹ and b² eachrepresents independently a hydrogen atom, a halogen atom, a cyano groupor a hydrocarbon group and R^(s) represents a hydrocarbon group; and atleast one one-functional macromonomer (M_(C)) having a weight-averagemolecular weight of not more than 1×10⁴, which contains one or moreunits having at least one polar group selected from the group consistingof --PO₃ H₂ --SO₃ H, --COOH, --PO(OH)R¹ [R¹ is a hydrocarbon group or--OR₂ (R² is a hydrocarbon group)] and a residue of a cyclic anhydridein its main chain and contains a group having polymerizable double bondrepresented by the formula (II): ##STR2## wherein V¹ represents --COO--,--OCO--, --CH₂ OCO--, --CH₂ COO--, --O--, --SO₂ --, --CO--, --CONHCOO--,--CONHCONH--, --CONHSO₂ --, --CON(T¹)--, --SO₂ N(T¹)-- or --C₆ H₅ --wherein T¹ represents a hydrogen atom or a hydrocarbon group, and b³ andb⁴ each represents independently a hydrogen atom, a halogen atom, acyano group, a hydrocarbon group, --COOZ¹ or --Z² --COOZ¹ wherein Z¹represents a hydrogen atom or a hydrocarbon group and Z² represents ahydrocarbon group, in only one end of the main chain;

the polymer (Q₂):

a graft type copolymer having a weight-average molecular weight of 1×10³˜2×10⁴ which contains at least one unit corresponding to one-functionalmacromonomer (M_(D)) which is a AB block copolymer composed of A and Bblocks and contains a polymerizable double bond at end of B block,wherein A block contains at least one unit having at least one polargroup selected from the group consisting of --PO₃ H₂, --SO₃ H, --COOH,phenolic hydroxyl group, --PO(OH)R¹ (R¹ has the same meaning as definedin formula (I)) and a residue of a cyclic anhydride and B block containsat least one unit represented by the formula (III): ##STR3## wherein V²represents --COO--, --OCO--, --(CH₂)_(a) OCO--, --(CH₂)_(a) COO-- (a isan integer of 1 to 3), --O--, --SO₂ --, --CO--, --CON(T¹)--, --SO₂N(T¹)--, --CONHCOO--, --CONHCONH-- or --C₆ H₅ -- (T¹ has the samemeaning as defined in formula (II)), R⁴ represents a hydrogen atom or ahydrocarbon group and b⁵ and b⁶ each has independently the same meaningas b¹ or b².

A photoconductive layer of the present invention may be any layerwherein a photoconductive compound is dispersed in a binder or a binderresin. Namely, there may be used a single layer type consisting of onlyone layer or a multilayer type (or function separated type) comprising acharge generating layer containing a photoconductive compound dispersedtherein and a charge transporting layer. It is most important in thepresent invention that the polymer (P) is distributed in the region nearthe surface facing the transfer layer, and the surface has improvedreleasability.

In the function separated type photoconductive layer, the chargetransporting layer which contacts with the transfer layer may containthe polymer (P) and the polymer (R), and the charge generating layer maycontain the photoconductive compound and the polymer (Q). Otherwise, inthe function separated type photoconductive layer, the chargetransporting layer which contacts with the transfer layer may containthe polymer (P), the polymer (Q), the polymer (R) and thephotoconductive compound.

The polymer (P) is preferably contained in the layer which contacts withthe transfer layer in an amount of 1 to 30% by weight based on the totalweight of the layer.

The polymer (Q) is preferably contained in the layer containing thephotoconductive compound in an amount of 1 to 100 parts by weight,preferably 3 to 50 parts by weight per 100 parts by weight of thephotoconductive compound.

The polymer (R) is preferably contained in the layer which contacts withthe transfer layer in an amount of 5 to 99.1% by weight based on thetotal weight of the layer.

Binder or binder resin is defined in the specification of the presentapplication, as a resin forming a matrix in which a photoconductivecompound is dispersed, including the polymer (P), the polymer (Q), andthe polymer (R), and other resins which may optionally be present in thephotoconductive layer.

Preferably, the photoconductive layer of the present invention containsphotosetting and/or thermosetting agent. The photosetting and/orthermosetting agent is defined in the specification of the presentapplication, as a compound, an oligomer or polymer which can be cured byat least one of light and heat, or a crosslinking agent.

The present invention further relates to a process for forming a colorproof wherein at least one color toner image is electrophotographicallyformed on the electrophotographic material for color proofing whichcomprises a substrate, a photoconductive layer and a transfer layer inthis order, and then transferred together with said transfer layer to asheet material to prepare the color proof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates schematically a heat transfer apparatus used in thepresent invention.

1 is a metalic roller coated with a rubber; 2 is a build-in heater; 3 isa means for detecting a surface temperature; 4 is a temperaturecontroller.

DETAILED EXPLANATION OF THE INVENTION

The presence of the polymer (P) in the region near the surface facingthe transfer layer imparts the releasability to the photoconductivelayer so that the transfer layer can easily be peeled-off from thephotoconductive layer.

When the solution for formation of the photoconductive layer containingthe polymers (P), the polymers (Q) and the polymers (R) is applied tothe substrate, the polymer (P) migrates to the top surface of the layer,and is condensed there to impart the releasability to the surface.Further, the polymer (P) is orientated putting the segment (X) towardthe transfer layer and putting the segment (Y) toward inside of thephotoconductive layer, since segment (Y) has high compatibility with thepolymer (R). Thus, the segment (X) provides the releasability to thesurface. The segment (Y) keeps the polymer (P) near the surface incooperation with the polymer (R). In other words, an anchor effect isattained by the polymer (P) and the polymer (R).

In addition, since the polymer (R) and the segment (Y) of the polymer(P) contain photo and/or thermosetting groups, and preferably, thephotoconductive layer contains the photo and/or thermosetting agent,both the polymer (P) and the polymer (R) are cured by light or heat andthe above mentioned orientation of the polymer (P) can be fixed.

As the result, when the transfer layer is coated on the photoconductivelayer, migration of the polymer (P) to the transfer layer is inhibitedto keep the interface between the transfer layer and the photoconductivelayer clear.

Accordingly, when the electrophotographic material for color proofing ofthe present invention is used for preparing a color proof, a multi-colortoner image formed electrophotographically is transferred together withthe transfer layer to a sheet material to prepare the color proof.

Further, a solvent used for coating a transfer layer may be selecteddepending on kinds of a thermoplastic resin used in the transfer layer.However, since some solvents have high solvating ability with binders ofthe photoconductive layer, they affect adversely the dispersion of thepolymer (P) in the photoconductive layer resulting in lowering ofelectrophotographic properties such as background contamination anddeterioration of image quality.

The above problem is solved by crosslinking of binders in thephotoconductive layer of the present invention to impart solventresistance thereto.

Since the layer containing the photoconductive compound contains thepolymer (Q) as a binder, the photoconductive compound can be finelydivided and dispersed uniformly in the layer. Further, even when thephotoconductive compound is spectrally sensitized by a sensitizing dye,the polymer (Q) can interact with the photoconductive compoundsufficiently irrespective of the kind of the sensitizing dye. Inparticular, in the system of the present invention, the photoconductivecompound can also interact-sufficiently with a sensitizing dye forsemiconductor laser beams, whereas it cannot interact with the dye inelectrophotographic materials using conventional binder resins.

Although,the present invention is not restricted by any theories, theabove effect seems to be attained by the fact that the polymer (Q) isadsorbed on the surface of the photoconductive compound particleswithout disturbing the interaction between the sensitizing dye and thephotoconductive compound, and keeps the dye coating on the surface ofthe photoconductive compound particles in good condition. As the result,it seems that electrophotographic properties can be kept good and stableeven when the environment condition changes significantly, for exampleto higher or lower temperature, or higher or lower humidity.

When the photoconductive layer is the single layer type, aphotoconductive compound, the polymer (Q), the polymer (R), and a smallamount of the polymer (P) are present together in one layer. In suchmulti-components layer, the polymer (Q) can also interact with thephotoconductive compound sufficiently without being disturbed by thepolymer (R) to impart excellent electrostatic properties to the layer.The polymer (P) can also migrate to the top surface of the layer toimpart excellent releasability to the surface of the layer.

The releasability of the photoconductive layer of the present inventionwas evaluated by tack strength measured by Pressure Sensitive Tape andSheet Test of JIS Z0237-1980. The tack strength may be not more than 150gram.force (g.f), preferably not more than 100 g.f, especially not morethan 50 g.f in order to obtain good releasability of the photoconductivelayer.

Pressure Sensitive Tape and Sheet Test of JIS Z0237-1980 is conductedusing the electrophotographic material for color proofing of the presentinvention wherein the transfer layer is not formed as the test plate anda pressure sensitive tape of the 6 mm wide are used for measuring in apeeling rate of 120 mm/min. Tack strength is calculated by convertingthe value measured with the tape of the 6 mm wide to the value for atape of the 10 mm. Tack strength of the surface of photoconductive layerafter forming the transfer layer is equal to that before forming thetransfer layer.

The substrate, the photoconductive layer, and the transfer layer of theelectrophotographic materials for color proofing of the presentinvention will be detailed below.

(The Substrate)

The substrate may be a known substrate. Preferably, the substrate isphotoconductive. Examples of the photoconductive substrate include: asubstrate made of metal, paper, or plastic, which is treated so as toget conductivity, for example, by being impregnated with a materialhaving low insulation resistivity; a substrate wherein conductivity isimparted to the reverse side thereof (the opposite side to the side onwhich the photosensitive layer is applied), and at least one coating isapplied thereon, for example, in order to inhibit curling; a substrate,wherein a water proof adhesive layer is applied on the surface thereof.;a substrate wherein at least one precoat layer is optionally applied onthe latter substrate; and a substrate which is a laminate on paper of aplastic sheet having conductivity on which a material such as aluminiumhas been vapor-deposited.

Examples of a conductive substrate or a substrate to which conductivityis imparted are described in the following references: Yukio Sakamoto,Electrophotographics,14, (No.1), pages 2-11, (1975); Hiroyuki Moriga,Chemistry of special papers, Polymer Publishers (1975); M. F. Hoover, J.Macromol. Sci. Chem. A-4 (6), 1327-1417 (1970).

(The Photoconductive Layer)

(The polymer (P))

The polymer (P) is selected from the group consisting of the polymers(P₁), (P₂), (P₃) and (P₄). All of them are block copolymers comprisingthe segment (X) and the segment (Y).

Preferably, the segment (X) contains not less than 80% by weight,especially not less than 90% by weight of the units having fluorineatom(s) and/or silicon atom(s) based on the total weight of the segment(X). Preferably, the segment (Y) contains 1 to 60% by weight, especially5 to 40% by weight of the units having the photo and/or thermosettinggroup(s) based on the total weight of the segment (Y).

The ratio by weight of the segment (X) to the segment (Y) in the polymer(P) may be 5-95 to 95-5, preferably 10-90 to 90-10.

The unit having fluorine atom(s) and/or-silicon atom(s) may preferablycontain at least three fluorine atoms if it does not contain a siliconatom. It may preferably contain at least two silicon atoms if it doesnot contain a fluorine atom. Further it may contain at leastone,fluorine atom and at least one silicon atom, if it contains both offluorine and silicon atoms.

(The polymer (P₁))

The following illustrates the polymer (P₁).

The polymer (P₁) is a linear block copolymer which contains at least onepolymer segment (X) containing not less than 50% by weight of unitshaving fluorine atom(s) and/or silicon atom(s) besed on the total weightof polymer segment (X) and at least one polymer segment (Y) containingunits having photosetting and/or thermosetting group(s);

The polymer (P₁) may be any type of linear block copolymers, such as ABtype block copolymer (such as, (X)--(Y)) or multi blocked polymerthereof, ABA type block copolymer ((such as (X)--(Y)--(X) or,(Y)--(X)'(Y)).

Weight-average molecular weight of the polymer (P₁) may be 5×10³ to1×10⁶, preferably 1×10⁴ to 5×10⁵. Preferably, weight-average molecularweight of segment (X) in the polymer (P₁) may be not less than 1×10³.

(The polymer (P₂))

The following description illustrates the polymer (P₂).

The polymer (P₂) is a star type copolymer which contains at least threeAB type block copolymer chains consisting of at least one polymersegment (X) containing not less than 50% by weight of units havingfluorine atom(s) and/or silicon atom(s) besed on the total weight ofpolymer segment (X) and at least one polymer segment (Y) containingunits having photosetting and/or thermosetting group(s), and said blockcopolymer chains are bonded through an organic group (z).

The segments. (X) and (Y) may be present in AB block polymer chain ofthe star type copolymer (P₂) in any order. Namely, the polymer (P₂) mayhave the following formulae: ##STR4## (Z is the organic group (Z), (X)is the segment (X), and (Y) is the segment (Y)).

At most fifteen, preferably not more than ten of AB type blockcopolymers may be linked to the organic group (Z).

Weight-average molecular weight of the polymer (P₂) may be 5×10³ to1×10⁶, preferably 1×10⁴ to 5×10⁵. Weight-average molecular weight of thesegment (X) in the polymer (P₂) is preferably not less than 1×10³.

The organic group (Z) may be any type of molecules having molecularweight of not more than 1000. Examples of the organic groups includehydrocarbon groups having not less than three valency such as thefollowing groups. ##STR5## r¹ to r⁶ each represents independently asingle bond, a hydrogen atom or a hydrocarbon group, provided that atleast one of r¹ and r² and at least one of r³ to r⁶ represent a singlebond or a group having a valency of not less than 2).

These hydrocarbon groups may be present either solely or in combination.In the latter case, the organic group (Z) may further contain linkinggroup(s) such as --O--, --S--, --N(r⁷)--, --COO--, --CON(r⁷)--, --SO₂--, --SO₂ N(r⁷)-- (r⁷ each represents independently a hydrogen atom or ahydrocarbon group), --NHCOO--, --NHCONH--, and a residue of aheterocyclic group having hetero atom(s) such as an oxygen atom, asulphur atom and a nitrogen atom (such as thiophene, pyridine, pyran,imidazole, benzimidazole, furan, piperidine, pyrazine, pyrrole,piperazine ring).

Examples of the linking groups further include a combination of theabove mentioned linking groups and a group selected from the groupconsisting of groups of the following formulae. However, the organicgroup (z) is not limited to those illustrated here. ##STR6## (Thepolymer (P₃)

The following illustrates the polymer (P₃).

The polymer (P₃) is a graft copolymer comprising at least one polymersegment (X) containing not less than 50% by weight of units havingfluorine atom(s) and/or silicon atom(s) and at least one polymer segment(Y) containing units having photosetting and/or thermosetting group(s);

Weight-average molecular weight of the polymer (P₃) may be 5×10³ to1×10⁶, preferably 1×10⁴ to 5×10⁵. Weight-average molecular weight of thesegment (X) in the polymer (P₃) is preferably not less than 1×10³.

The segments (X) and (Y) may be present in the polymer (P₃) in anyorder. Namely, the polymer (P₃) may have the following formulae:##STR7## (The polymer (P₄))

The following illustrates the polymer (P₄). The polymer (P₄) is an ABtype or ABA type block copolymer comprising at least one polymer segment(X) containing not less than 50% by weight of units having fluorineatom(s) and/or silicon atom(s) and at least one polymer segment (Y)containing units having photosetting and/or thermosetting group(s), andat least one of said polymer segment (X) is the following graft typepolymer segment (X'), at least one of said polymer segment (Y) is thefollowing graft type polymer segment (Y'), or at least one of saidpolymer segment (X) is the following graft type polymer segment (X') andat least one of said polymer segment (Y) is the following graft typepolymer segment (Y'):

The graft type polymer segment (X'): a polymer segment which has aweight-average molecular weight of 1×10³ ˜2×10⁴, and comprises at leastone macromonomer segment (M_(A)) which contains not less than 50% byweight, preferably not less than 90% by weight of units having fluorineatom(s) and/or silicon atom(s);

The graft type polymer segment (Y'): a polymer segment which has aweight-average molecular weight of 1×10³ ˜2×10⁴, and comprises at leastone macromonomer segment (M_(B)) which does not contain units havingfluorine atom(s) and/or silicon atom(s);

The segments (X) and (Y) may be present in the block copolymer (P₄) inany order. Namely, the polymer (P₄) may have the following formulae:##STR8##

The segment (X) may contain the macromonomer segment (M_(A)) in anamount of 1-50% by weight, preferably 3-30% by weight based on the totalweight of the segment (X).

The segment (Y) may contain the macromonomer segment (M_(B)) in anamount of 1-50% by weight, preferably 3-30% by weight based on the totalweight of the segment (Y).

Preferably, the macromonomer segment (M_(B)) contains the units havingphoto and/or thermosetting group(s) in an amount of 1-50% by weight,preferably 3-20% by weight based on the total weight of the macromonomersegment (M_(B)).

Weight-average molecular weight of the polymer (P₄) may be 5×10³ to1×10⁶ preferably 1×10⁴ to 5×10⁵. Weight-average molecular weight of thesegment (X) in the polymer (P₄) is preferably not less than 1×10³.

The following illustrates the segment (X) and the segment (Y) more indetail.

The units having fluorine atom(s) and/or silicon atom(s) may containsubstituent(s) having fluorine atom(s) and/or silicon atom(s). Thesubstituent(s) may present in a main chain of the polymer (P), or maypresent in side chains thereof.

Examples of the substituent having fluorine atom(s) include: --C_(b)F_(2b+1) (b is an integer of 1 to 18), --(CF₂)_(c) CF₂ H (c is aninteger of 1 to 17), --CFH₂, mono-valent organic groups of the followingformulae: ##STR9## --CF₂ --, --CFH-- and di-valent organic groups of thefollowing formulae: ##STR10##

Examples of the group having silicon atom(s) include mono-valent ordi-valent organic groups of the following formulae:

    --Si(R.sup.5)(R.sup.6)(R.sup.7) and --Si(R.sup.8)(R.sup.9)--.

R⁵, R⁶, R⁷, R⁸ and R⁹ may be same or different, each represents ahydrocarbon group having 1 to 22 carbon atoms which can be substituted,an organic residue having fluorine atom(s) mentioned above, --OR' (R'represents a hydrocarbon group having 1 to 22 carbon atoms which can besubstituted), or --OSi(R^(5'))(R^(6') (R^(7'))(R^(5'), R^(6') and R^(7')each represents independently a hydrocarbon group having 1 to 22 carbonatoms which can be substituted, an organic residue having fluorineatom(s) mentioned above, --OR' (R' has the same meaning as definedabove). Examples of R⁵ to R⁹, R', and R^(5') to R^(7') include: an alkylgroup having 1 to 18 carbon atoms which can be substituted (such asmethyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl,2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 2-cyanoethyl,3,3,3-trifluoropropyl, 2-methoxyethyl, 3-bromopropyl,2-methoxycarbonylethyl, 2,2,2,2',2',2'-hexafluoroisopropyl), an alkenylhaving 4 to 22 carbon atoms which can be substituted (such as2-methyl-1-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl,1-pentenyl, 1-hexenyl, 2-hexenyl, 4-methyl-2-hexenyl), an aralkyl grouphaving 7 to 12 carbon atoms which can be substituted (such as benzyl,phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl,chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl,dimethylbenzyl, dimethoxy benzyl), an alycyclic group having 5 to 8carbon atoms which can be substituted (such as cyclohexyl, 2-cyclohexyl,2-cyclopentylethyl), or a substituted or unsubstituted aromatic grouphaving 6 to 12 carbon atoms (such as phenyl, naphthyl, tolyl, xylyl,propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl,ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl,dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl,methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl,acetoamidephenyl, propioamidephenyl, dodecyloylamidephenyl).

The substituent having fluorine atom(s) and the substituent havingsilicon atom(s) can be combined each other directly or through a linkinggroup.

Examples of the linking group include di-valent groups such as --O--,--S--, --NR⁵ --, --SO--, --SO₂ --, --COO--, --OCO--, --CONHCO--,--NHCONH--, --CONR⁵ --, --SO₂ NR⁵ --, a di-valent aliphatic or aromaticgroup, or a combination of these di-valent groups. R⁵ is the samemeaning as defined above.

Examples of di-valent aliphatic groups include: ##STR11## (e₁ and e₂each represents independently a hydrogen atom, a halogen atom (such as achlorine atom and a bromine atom), or an alkyl group having 1 to 12carbon atoms (such as methyl, ethyl, propyl, chloromethyl, bromomethyl,butyl, hexyl, octyl, nonyl and decyl), and Q represents --O--, --S--, or--NR¹⁰ -- wherein R¹⁰ represents an alkyl group having 1 to 4 carbonatoms, --CH₂ Cl or --CH₂ Br).

Examples of di-valent aromatic groups include: a residue of benzene, aresidue of naphthalene, and a heterocyclic group with 5 or 6 members(containing at least one hetelo atom selected from the group consistingof an oxygen atom, a sulfur atom, and a nitrogen atom). These aromaticgroups may be substituted, for example, by a halogen atom (such as afluorine, chlorine or bromine atom), an alkyl group having 1 to 8 carbonatoms (such as methyl, ethyl, propyl, butyl, hexyl, octyl), an alkoxygroup having 1 to 6 carbon atoms (such as methoxy, ethoxy, propoxy,butoxy).

Examples of heterocyclic groups include furan, thiophene, pyridine,pirazine, piperazine, tetrahydrofuran, pyrrole, tetrahydropyran,1,3-oxazoline rings.

The followings ((a-1)-(a-33)) are examples of the units having fluorineatom(s) and/or silicon atom(s). They should not be understood aslimitation of the present invention.

In the examples, --Rf represent the following substituents;

1) --C_(d) F_(2d+1)

2) --CH₂ C_(d) F_(2d+1)

3) --CH₂ CH₂ C_(d) F_(2d+1)

4) --CH₂ (CF₂)_(d) CFHCF₃

5) --CH₂ CH₂ (CF₂)_(d) CFHCF₃

6) --CH₂ CH₂ (CF₂)_(d) CFHCF₂ H

7) --CH₂ (CFH)_(d) CF₂ H

8) --CH(CF₃)₂, ##STR12##

In the above and below formulae, d is an integer of 1 to 18, e is aninteger of 1 to 5, and b is a hydrogen atom or a methyl group. ##STR13##

The following illustrates the macromonomer segment (M_(A)).

The macromonomer segment (M_(A)) has a weight-average molecular weightof 1×10³ to 2×10⁴. A weight-average molecular weight of less than 1×10³results in too short graft parts causing lower effect of releasabilityof the photoconductive layer. A weight-average molecular weight of morethan 1×10³ results in lower reactivity with monomers corresponding toother units, which causes that desirable graft copolymer cannot beobtained.

The macromonomer segment (M_(A)) may be one corresponding to amacromonomer which may contain the above mentioned units having fluorineatom(s) and/or silicon atom(s) mentioned for the segment (X). It maycontain a group having polymerizable double bond represented by thefollowing formula (IV) in one end of a main chain thereof:

    CH(a.sup.1)═C(a.sup.2)--V.sup.3 --                     (IV)

wherein

a¹ and a² each represents independently a hydrogen atom, a halogen atom,a trifluoromethyl group, a cyano group, or a hydrocarbon group. V³represents --COO----OCO--, --(CH₂)_(f) OCO--, --(CH₂)_(f) COO-- (f is aninteger of 1 to 3), --O--, --SO₂ --, --CO--, --CON)T¹)--, --SO₂ N(T¹)--,--CONHCOO--, --CONHCONH--, or --C₆ H₄ --, T¹ is a hydrogen atom, or ahydrocarbon group.

Examples of a hydrocarbon group as T¹ include: a substituted orunsubstituted alkyl group having 1 to 18 carbon atoms (such as methyl,ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, hexadecyl,octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl,2-methoxycarbonylethyl, 2-methoxyethyl, 3-bromopropyl, an alkenyl grouphaving 4 to 18 carbon atoms which may be substituted (such as2-methyl-1-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl,1-pentenyl, 1-hexenyl, 2-hexenyl, 4-methyl-2-hexenyl), an aralkyl grouphaving 7 to 12 carbon atoms which may be substituted (such as benzyl,phenethyl, 3-phenylpropyl, naphtylmethyl, 2-naphtylethyl, chlorobenzyl,bromobenzyl, methyl benzyl, ethyl benzyl, methoxy benzyl,dimethylbenzyl, dimethoxy benzyl), an alicyclic group having 5 to 8carbon atoms which may be substituted (cyclohexyl, 2-cyclohexylethyl,2-cyclopentylethyl), an aromatic group having 6 to 12 carbon atoms whichmay be substituted (such as phenyl, naphthyl, tolyl, xylyl,propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl,ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl,dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl,methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl,acetamidophenyl, propioamidophenyl, dodecyloylamidophenyl.

If V³ is --C₆ H₄ --, the benzene ring may have substituent(s). Thesubstituents may be a halogen atom (such as a chlorine and bromineatom), an alkyl group (such as methyl, ethyl, propyl, butyl,chloromethyl and methoxymethyl) or an alkoxy group (such as methoxy,ethoxy, propoxy, butoxy).

Preferably, a¹ and a² each represents independently a hydrogen atom; ahalogen atom (such as a chlorine atom and a bromine atom); atrifluoromethyl group; a cyano group; or an alkyl group having 1 to 4carbon atoms (such as methyl, ethyl, propyl and butyl), --COOZ³, or --Z²--COOZ³ wherein Z³ represents a hydrogen atom or an alkyl group having 1to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, anaralkyl group having 7 to 18 carbon atoms, an alicyclic group having 3to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms whichmay be substituted by the same group(s) groups as exemplified for T¹,and Z² is a hydrocarbon group.

Preferably, Z² may be methylene, ethylene, or propylene.

Especially, in the formula (IV), V³ may be --COO--, --OCO--, --CH₂OCO--, --CH₂ COO--, --O--, --CONH--, --C₆ H₄ --, a¹ and a² may be sameor different, a hydrogen atom, a hydrocarbon group having 1 to 6 carbonatoms (such as methyl, ethyl, propyl, butyl and hexyl). More preferably,one of a¹ and a² may be a hydrogen atom.

The group containing polymerizable double bond of the formula (IV) maybe bonded to the end of the macromonomer either directly or through alinking group. The linking group may be di-valent organic groups such as--O--, --S--, --Nd¹ --, --SO--, --SO₂ --, --COO--, --OCO--, --CONHCO--,--NHCONH--, --CONd² --, --SO₂ Nd³ --, --Si(d⁴)(d⁵)-- a di-valentaliphatic or aromatic group, or a combination of these di-valent groups.d¹, d², d³, d⁴ and d⁵ each represents independently the same group asexemplified for T¹ in the formula (IV).

Examples of di-valent aliphatic groups include: --C(k¹)(k²)--,--C(k¹)═C(k²)--, --C.tbd.C--, --C₆ H₁₀ -- and ##STR14## (k¹ and k² eachrepresents independently a hydrogen atom, a halogen atom (such as afluorine atom, a chlorine atom and a bromine atom), or an alkyl grouphaving 1 to 12 carbon atoms (such as methyl, ethyl, propyl,chloromethyl, bromomethyl, butyl, hexyl, octyl, nonyl and decyl)).

Examples of di-valent aromatic groups include: a residue of benzene, aresidue of naphthalene, and a hetelocyclic group with 5 or 6 members(containing as at least one hetero atom which consists a heterocyclicgroup selected from the group consisting of an oxygen atom, a sulfuratom and a nitrogen atom). These aromatic groups may be substituted, forexample, by a halogen atom (such as a fluorine atom, a chlorine atom anda bromine atom), an alkyl group having 1 to 8 carbon atoms (such asmethyl, ethyl, propyl, butyl, hexyl and octyl), an alkoxy group having 1to 6 carbon atoms (such as methoxy, ethoxy, propoxy and butoxy).

Examples of heterocyclic groups include furan, thiophene, pyridine,pirazine, piperazine, tetrahydrofuran, pyrrole, tetrahydropyran,1,3-oxazoline, pyrrolidine, piperidine rings or the group represented bythe following formulae: ##STR15## wherein Q is --O--, --S-- or --NR¹⁰ --(R¹⁰ is an alkyl group having 1 to 4 carbon atoms, --CH₂ Cl or --CH₂Br).

Examples of moietys which are formed by linking various organic residuesto units containing group(s) having a polymerizable double bondrepresented by the formula (II) include groups represented by thefollowing formulae: ##STR16## wherein P₁ is --H, --CH₃, --CH₂ COOCH₃,--Cl, --Br or --CN, P₂ is --H or --CH₃, b is --H or --CH₃, X is --Cl or--Br, n is an integer of 2 to 12, and m is an integer of 1 to 4.

(The segment (Y))

The following illustrates the units having photo and/or thermosettinggroup(s) in the segment (Y).

A photo and/or thermosetting group is a group which causes a curingreaction of the polymer by at least one of heat and light.

Examples of the photosetting group may be functional groups used inknown photosensitive polymers such as those described in the followingliteratures: Hideo Inui, Gentaro Nagamatsu, "Photosensitive Polymer"published by Kodansha, 1977; Takahiro Tsunoda, "New PhotosensitivePolymer", the publishing department of the Printing Society of Japan,1981; G. E. Green and B. P. Strak, J. Macro. Sci. Reas. Macro. Chem.,C21(2), 187-273 (1981-82); C. G. Rattey, "Photopolymerization of SurfaceCoatings", A. Wiley Inter Science Pub., 1982.

Examples of the thermosetting group may be functional groups in polymersdescribed in the following literatures: Tsuyoshi Endo, "Densifying ofThermosetting Polymer", C.M.C. Co.,Ltd.,1986; Yuji Harazaki, "The Latestbinder techniques handbook", chapter II-I, Sogogijutu center, 1985;Takayuki Otsu, "Synthesis, Design and New Use of Acrylic Resin, thepublishing department of Chubukeieikaihatsu center, 1985; Eizo Omori,"Functional Acrylic resins", Technosystem, 1985.

Examples of such groups include --COOH, --PO₃ H₂, --SO₂ H, --OH, --SH,--NH₂, --NHR¹² (R¹² is a hydrocarbon group, preferably having 1 to 8carbon atoms (such as methyl, ethyl, propyl, butyl, hexyl, octyl,2-chloroethyl, 2-methoxyethyl, 2-cyanoethyl)), a residue of a cyclicacid anhydride, --CONHCH₂ OR¹³ (R¹³ is a hydrogen atom or an alkyl groupsuch as those mentioned above), --N═C═O), groups of the followingformulae: ##STR17## (Z' is an atomic group which is necessary to form aheterocyclic ring together with the nitrogen atom, and the ring is aprotective group for --N═C═O), a silane coupling group, a titanatecoupling group, --Cd⁶ ═CHd⁷ (d⁶ and d⁷ each represents independently ahydrogen atom, a halogen atom (such as a chlorine atom and a bromineatom) or an alkyl group having 1 to 4 carbon atoms (such as methyl andethyl).

Examples of groups having the polymerizable double bond include CH₂═CH--, CH₂ ═CH--CH₂ --, CH₂ ═CHCOO--, CH₂ ═C(CH₃)--COO--, CH₃--CH═COO--, CH₂ ═CH--CONH--, CH₂ ═C(CH₃)--CONH--, CH₃ --CH═CH--CONH--,CH₂ ═CH--O--CO--, CH₂ ═C(CH₃)--OCO--, CH₂ ═CH--CH₂ --OCO--, CH₂═CH--NHCO--, CH₃ ═CH--CH₂ --NHCO--, CH₂ --CH--SO₂ --, CH₂ ═CH--CO--, CH₂═CH--O--, CH₂ ═CH--S--, groups of the following formulae: ##STR18##

The following description illustrates the macromonomer segment (M_(B)).

Weight average molecular weight of the macromonomer corresponding to themacromonomer segment (M_(B)) is in the range of 1×10³ to 2×10⁴,preferably 3×10³ to 1×10⁴. Weight average molecular weight of less than1×10³ results in an insufficient anchor effect. Weight average molecularweight of more than 2×10⁴ results in too poor reactivity forcopolymerization of the macromonomer with other monomers correspondingto the other units which constitutes the segment (Y).

The units constituting the macromonomer segment (M_(B)) may be any unitswhich do not contain a fluorine atom or a silicon atom. Preferably, themacromonomer segment (M_(B)) contain 1 to 50% by weight of the unitshaving photo and/or thermosetting group(s) based on the total weight ofthe macromonomer segment (M_(B)).

Examples of the photo and/or thermosetting group may be the same asdescribed above for the photo and/or thermosetting group in the segment(Y) other than the group having a polymerizable double bond.

(Other units)

Other units in the segments (X) and (Y) in the polymer (P) of thepresent invention may be any units corresponding to monomers which arecopolymerizable with the monomers corresponding to the above mentionedunits. Examples of them include units of addition polymer, polyester,polyether and polyimine.

The unit of the addition polymer may be those selected from units of thefollowing formula (V):

    --(CH(a.sup.1)--C(V.sup.3 --T.sup.1)(a.sup.2))--           (V)

In formula (V), a¹, a², V³ and T¹ are the same as defined in formula(IV) respectively.

The unit of the formula (V) is contained in the segment (X) in an amountof not more than 50% by weight, preferably not more than 20% by weight.More preferably, it is not contained.

The unit of the formula (V) is contained in the segment (M_(A)) in anamount of not more than 50% by weight, preferably not more than 20% byweight. More preferably, it is not contained.

The unit of the formula (V) is contained in the segment (Y) in an amountof 0 to 95% by weight, preferably 5 to 90% by weight based on the totalweight of the segment (Y).

The units of the formula (V) is contained in the segment (M_(B)) in anamount of 40 to 100% by weight, preferably 50 to 95% by weight.

Examples of other units which can be contained with the unit of formula(V) include units corresponding to monomers copolymerizable with themonomer corresponding to the unit of the formula (v), such as unitscorresponding to acrylonitrile, methacrylonitrile and vinyl heterocycliccompounds (such as vinyl pyridine, vinyl imidazole, vinyl pyrrolidone,vinyl thiophene, vinylpyrazole, vinyldioxane and vinyloxadine). Theseother units are contained in an amount of less than 20 parts by weightbased on 100 parts by weight of the polymer (p).

Further, the unit which contains at least one polar group selected fromthe group consisting of --PO₃ H₂, --SO₃ H, --COOH, --PO(OH)R¹³ (R¹³ is ahydrocarbon group or --OR¹⁴ (R¹⁴ is a hydrocarbon group)) and a residueof a cyclic anhydride can be contained in the segment (Y) in the polymer(P) in an amount of less than 10% by weight based on the total weight ofthe segment (Y).

Preferably, R¹³ and R¹⁴ each represents independently a hydrocarbongroup having 1 to 6 carbon atoms which may be substituted (such asmethyl, ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl,2-fluoroethyl, 3-chloropropyl, 3-methoxypropyl, 2-methoxy butyl, benzyl,phenyl, propenyl, methoxymethyl, ethoxymethyl and 2-ethoxyethyl).

Further, a residue of a cyclic anhydride may be a residue of analiphatic dicarboxylic anhydride or an aromatic dicarboxylic anhydride.

Examples of the aliphatic dicarboxylic anhydrides include succinicanhydride, glutaconic anhydride, maleic anhydride,cyclopentane-1,2-dicarboxylic anhydride, cyclohexene-1,2-dicarboxylicanhydride and 2,3-bicyclo[2,2,2]octadicarboxylic anhydride. These cyclicanhydrides may be substituted, for example, by a halogen atom such as achlorine atom and a bromine atom and an alkyl group such as methyl,ethyl, butyl and hexyl.

Further, examples of aromatic dicarboxylic anhydrides include phthalicanhydride, naphthalene-dicarboxylic anhydride, pyridine-dicarboxylicanhydride and thiophene-dicarboxylic anhydride. These cyclic anhydridesmay be substituted, for example, by a halogen atom such as a chlorineatom and a bromine atom and an alkyl group such as methyl, ethyl,propyl, butyl; hydroxy; cyano; nitro; and alkoxycarbonyl (alkoxy may be,for example, methoxy and ethoxy).

The above mentioned units may be any units corresponding to vinyliccompounds having polar group(s) which can be copolymerized with, forexample, a monomer corresponding to the unit of the formula (IV). Thevinylic compounds are described in, for example, Polymer Society ofJapan, "Polymer data handbook (fundamentals)" published by Baifukan,(1986). Examples of the compounds include acrylic acids, α and/orβ-substituted acrylic acid (such as α-acetoxy acrylic acid,α-acetoxymethyl acrylic acid, α-(2-amino)ethyl acrylic acid, α-chloroacrylic acid, α-bromo acrylic acid, α-fluoro acrylic acid,α-tributylsylil acrylic acid, α-cyano acrylic acid,β-chloro acrylicacid, β-bromo acrylic acid, α-chloro-β-methoxy and α,β-dichloro acrylicacid), methacrylic acid, itaconic acid, semi ester of itaconic acid,semi amides of itaconic acid, crotonic acid, 2-alkenylcarboxylic acids(such as 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid,4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid), maleic acid, semiesters of maleic acid, semi amides of maleic acid, vinyl benzenecarboxylic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid, vinylphosphonic acid, vinyl- or allyl-semi ester of dicarboxylic acids, andesters and amides of these carboxylic acids and sulfonic acids, whichcontain polar group(s) as substituent(s).

(Preparation of the polymer (P))

The polymers (P) or the one-functional macromonomer corresponding to themacromonomer segment(s) (M_(A)) or (M_(B)) may be prepared in accordancewith known polymerization methods, for example, methods described in thefollowing literatures: W. J. Burlant, A. S. Hoffman "Block and GraftPolymer" (1986, Renhald), R. J. Ceresa, "Block and Graft Polymers"(1962, Butterworths), D. C. Allport, W. H. James "Block Copolymers"(1972, Applied Sci), A. Noshay, J. F. McGvath "Block Copolymers" (1977,Academic press.), G. Huvtrez D. J. Wilson, G. Riess, NATO ASI Sev. Sev.E. 1985, 149, V. Percea, Applied. Polymer Sci. 285, 95 (1985).

Ionic polymerization reactions wherein alkyl lithium, lithiumdiisopropylamide, alkali metal alcoholates, alkyl magnesium halides,alkyl aluminium halides etc. are used as a polymerization initiator aredescribed in the following literatures: T. E. Hogeu-Esch, J. Smid,"Recent Advances in Anionic Polymerization" (1987, Elsevier, N.Y.),Yoshio Okamoto, Polymer, 38,912 (1989), Mitsuo Sawamoto, Polymer,38,1018, (1989), Tadashi Narita, Polymer, 37, 252 (1988), B.C. Anderson, etal, Macromolecules 14, 1601(1981), S. Aoshima, T. HigashimuraMacromolecules 22, 1009(1989) etc.

Ionic polymerization reactions with hydrogen iodide/iodine system etc.are described in Macromol. Chem., Macromol. Symp., 13/14, 457(1988),Toshinobu Higashimura, Mitsuo Sawamoto, papers for Polymer, 46, 189(1989).

Group transfer polymerization reactions are described in D. Y. Sogah etal, Macromolecules 20, 1473 (1987), O. W. Webster, D. Y. Sogah, Polymer,36, 808(1987), M. T. Reetg, et al, Angew. Chem. Int. Ed. Eugl. 25,9108(1986), J. P. KOKAI No. Sho 63-97609 etc.

Further, living polymerization reactions with porphyrin metal complexare described in T. Yasuda, T. Aida, S. Inoue, Macromolecules, 17, 2217(1984), M. Kuroki, T. Aida, S. Inoue, J. Auu Chem. Soc. 109, 4737(1987), M. Kuroki et al, Macromolecules, 21, 3115 (1988.), M. Kuroki, I.Inoue, Organic Synthesis, 47, 1017 (1989) etc.

Ring opening polymerizations of cyclic compounds are described in thefollowing literatures: S. Kobayashi, T. Saegusa, "Ring OpeningPolymerization" (1984, Applied Science Publishors, Co.,Ltd.), W.Seeliger et al. Angew. Chem. Int. Engl. 5, 875 (1966), S. Kobayashi etal, Poly, Bull. 13, 447 (1985), Y. Chujo et al, Macromolecules, 22,1074, (1989) etc.

Further, photo living polymerization reactions wherein dithiocarbamatecompound or xanthate compound are used as initiator are described in thefollowing literatures: Takayuki Otsu, Polymer, 37, 248 (1988), ShunichiHinoemori, Takaiti Otsu, Polym. Rep. Jap.37, 3508 (1988), J. P. KOKAINos. Sho 64-111 and Sho 64-26619, M. Niwa, Macromolecules, 189, 2187(1988) etc.

Methods for preparation of block copolymer by radical polymerizationreaction wherein a polymer containing azo groups or peroxide groups isused as initiator are described in the following literatures: Akira Uedaet al, Papers for Polymer, 33,931 (1976), Akira Ueda, Reports by OsakaCity Industrial Laboratory, 84, (1989), O. Nuyken et al, Macromol. Chem.Rapid. Commun, 9, 671 (1988), Yasuo Moriya et al, Reinforced Plastics,29, 907 (19), Ryohei Oda, Science and Industry, 61, 43(1987) etc.

Methods for preparation of a graft type block copolymer are described inthe following literatures in addition to the above literatures: FumioIde, "Graft polymerization and application thereof" (1977, Polymerpublishers); Polymer Society of Japan, "Polymer alloy" (1981, TokyoKagaku Doujin) etc.

Those methods include, for example, a method for grafting a polymerchains by a mechanochemical reaction with polymerization initiator,chemical active beam (such as radiation and electron rays) andmechanical application, a method for grafting polymer chains withfunctional groups in other polymer chains through chemical bond(reaction between polymers), or a method for grafting by polymerizationof macromonomers.

Methods for grafting polymer chains by the reaction between polymers aredescribed in the following literatures: T. Shiota et al, J. Appl. Polym.Sci. 13, 2447 (1969), W. H. Buck Rubber Chemistry and Technology, 50,109 (1976); Tsuyoshi Endo, Tsutomu Yokozawa, Journal of Japan AdhesiveSociety (Nihonsechakukyokaishi), 24, 323 (1988), Tsuyoshi Endo, ibid,25, 409, (1989) etc.

Methods for grafting by polymerization of macromonomer described in thefollowing literatures: P. Dreyfuss & R. P. Quirk, Encycl. Polym. Sci.Eng., 7, 551 (1987), P. F. Rempp, E. Franta, Adv. Polym. Sci., 58, 1(1984), V. Percec, Appl. Poly. Sci.,285, 95 (1984), R. Asami, M. Takari,Macromol. Chem. Suppl., 12, 163 (1985), R. Rempp., et al, Macromol.Chem. Suppl., 8, 3 (1984), Yushi Kawakami, Chemical Industry, 38, 56(1987), Yuya Yamashita, Polymer, 31, 988 (1982), Shiro Kobayashi,Polymer, 30, 625 (1981), Toshinobu Higashimura, Journal of JapanAdhesive Society, 18, 536 (1982), Koichi Ito, Polymer Processing, 35,262 (1986), Shiro Toki, Takashi Tsuda, functional materials, 1987, No.10, 5; Yuya Yamashita, "Chemistry and Industry of Macromonomer" (1989,I.P.C Co.,Ltd.) Tsuyoshi Endo, "Design of Construction for NovelFunctional Polymer", Chapter 4, (1991, CMC Co., Ltd.; Y. Yamashita etal. Polym. Bull. 5, 361 (1981) etc.

Methods for preparation of a star type block copolymer are described inthe following literatures: M. T. Reetz Angew. Chem. Int. Ed. Engl 27,1373 (1988), M. Sgwarc, "Carbanions, Living Polymers and ElectronTransfer Processes" (1968. Wiley. New York), B. Gordon etal, Polym.bull. 11, 349 (1984), R. B. Bates et al. J. Org. Chem. 44, 3800 (1979),Y. Sogah, A. C. S. Polym. Repr. 1988, No.2, 3, J. W. Mays. Polym. Bull.23, 247 (1990), I. M. Khan. et al. Macromolecules, 21, 2684 (1988), A.Morikawa Macromolecules, 24, 3469 (1991), Akira Ueda, Susumu Nagai,Polymer, 39, 202 (1990), T. Otsu, Polym. Bull. 11, 135 (1984) etc.

Methods for preparation of star type block copolymer are also describedin the following literatures: W. J. Burlant, A. S. Hoffman, "Block andGraft Polymers" (1960, Renhold), R. J. Ceresa, "Block and GraftCopolymers" (1962, Butterwords) L. C. Allport, W. H. James, "BlockCopolymers" (1972, Applied Sci), A. Noshay, J. E. McGrath "BlockCopolymers" (1977, Academic press.) et al.

Further, the star type copolymer used in the present invention can beprepared by known method for preparing a star type polymer whereinmonomers having polar group(s) and group(s) containing polymerizabledouble bonds are used. Examples of the known method include apolymerization reaction wherein carbanion is used as initiator. Specificexamples of the methods are described in the following literatures: M.Morton, T. E. Helminiak et al, J. Polym. Sci., 57, 471 (1962), B. GordonIII, M. Blumenthal, J. E. Loftus et al, Polym. Bull., 11, 349 (1984), R.B. Bates, W. A. Beavers et al, J. Org. Chem., 44, 3800 (1979).

For the preparation of the polymer (P) containing particular polargroups such as --COOH in the segment (Y), the polar groups incorresponding monomers should be protected by a protective group, and ablock copolymer is prepared by living polymerization reaction such asionic polymerization by organic metal compounds (such as alkyl lithiums,lithium diisopropylamide, alkyl magnesium halides) or hydrogeniodide/iodine or photopolymerization wherein porphyrin metal complex isused as a catalyst or group transition polymerization. After thepolymerization reaction, the protective group should be released througha hydrolysis, hydrogenation, oxidative degradation or photodegradationreaction. One example of the reactions is illustrated by the followingreaction formula (1). ##STR19##

The macromonomers corresponding to the macromonomer segments (M_(A)) and(M_(B)), and the polymer (P) comprising at least one of the macromonomersegments (M_(A)) and (M_(B)) can be prepared by the known method ofpolymerization.

For example, the macromonomers can be prepared by preparing a polymerhaving the weight average molecular weight of not more than 2×10⁴ byknown polymerization methods, for example, ionic polymerization reactionwith organic metal compounds (such as alkyl lithiums, lithiumdiisopropylamide, alkyl magnesium halides) or hydrogen iodide/iodine,photopolymerization wherein porphyrin metal complex is used as acatalyst, group transition polymerization, photo initiatorpolymerization reactions wherein dithiocarbamate compound or xanthatecompound are used as initiator, radical polymerization reaction using aradical initiator (such as azobis compound and peroxide compound) andchain transfer agent (such as mercapto compounds and iodo compounds),and then introducing a group having polymerizable double bond-to one endof the resultant polymer with various reagents.

For example, the living polymers can be easily prepared by a method inaccordance with the following literature: P. Lutz, P. Masson et al.,Polym. Bull.,12, 79(1984) B. C. Anderson, G. D. Andrews et. al.,Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute. et al., Polym. J.17, 977 (1985), 18, 1037(1986), Koichi Migite, Koichi Hatada,Kobunshikako, 36, 366(1987), Toshinobu Higashimura, Mitsuo Sawamoto,papers for Polymer, 46, 189 (1989), M. Kuroki, T. Aida, T. Am. Chem.Soc. 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Yukigoseikagaku, 43,300(1985), D. Y. Sogah, W. R. Hertler et al., Macromolecules, 20,1473(1987), Takayuki Otsu, Polymer, 37, 248 (1988), Shunichi Hinoemori,Takaiti Otsu, Polym. Rep. Jap. 37, 3508 (1988), J. P. KOKAI Nos. Sho64-111 and Sho 64-26619.

Examples for radical polymerization method are described in: Y.Yamashita, J.Appl. Polym. Sci, Appl. Polym. Symp,36, 193(1981), K. K.Roy et al., Makromol. Chem. 153, 71 (1972), Y. Yamashita et al., Polym.J., 14, 255(1982), Akira Ueda, Susumu Nagai, Kagaku to Kogyo,60,57(1986).

Methods for introducing the group having-polymerizable double bond toone end of the polymer are known in the art. Such methods are describedin the following literatures and references cited therein: P. Dreyfuss &R. P. Quirk, Encycl. Polym. Sci. Eng., 7, 551 (1987), P. F. Rempp, E.Franta, Adv. Polym. Sci., 58, 1 (1984), V. Percec, Appl. Poly. Sci.,285,95 (1984), R. Asami, M. Takari, Macromol. Chem. Suppl., 12, 163 (1985),P. Rempp., et al, Macromol. Chem. Suppl., 8, 3 (1984), Yushi Kawakami,Chemical-Industry, 38, 56 (1987), Yuya Yamashita, Polymer, 31, 988(1982), Shiro Kobayashi, Polymer, 30, 625 (1981), Toshinobu Higashimura,Journal of Japan Adhesive Society, 18, 536 (1982), Koichi Ito, PolymerProcessing, 35, 262 (1986), Shiro Toki, Takashi Tsuda, functionalmaterials, 1987, No. 10, 5; Yuya Yamashita, "Chemistry and Industry ofMacromonomer" (1989, I.P.C Co.,Ltd.).

For the preparation of the macromonomer containing particular polargroups mentioned above, the polar groups in corresponding monomersshould be protected by a protective group, and the protective groupshould be released after polymerization and introduction of the grouphaving a polymerizable double bond.

Protection by the protective group and release of the protective groupcan be conducted easily by known techniques. Such methods are describedin the following references in addition to the foregoing literatures:Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer", Kodansha Co.,Ltd.(1977), T. W. Green, "Protective Groups in Organic Synthesis", JohnWiley & Sons (1981), J. F. W. Mc Omie, "Protective Groups in OrganicChemistry" Plenum Press, (1973) etc.

The polymer (P₄) can also be prepared by known living polymerizationsuch as ionic polymerization, group transition polymerization, porphyrinmetal polymerization and photoinitiator polymerization.

Polymer (P₄) can also be prepared by radical copolymerization usingpolymeric azo initiators described in the following references: AkiraUeda, Susumu Nagai et al., Kobunshi Ronbunshu,33, 131(1976), Akira Ueda,Susumu Nagai et al., Kagaku to Kogyo, 64, 446(1990).

(The polymer (Q))

The following illustrates the polymer (Q), namely the polymer (Q₁) andthe polymer (Q₂).

(The polymer (Q₁))

As explained above, the polymer (Q₁) is a graft type copolymer obtainedby polymerizing at least one monomer represented by the formula (I) andat least one one-functional macromonomer (M_(C)) having at least onepolar group.

The weight-average molecular weight of the polymer (Q₁) is 1×10³ to2×10⁴, preferably 3×10³ to 1×10⁴. The glass transition temperature ofthe polymer (Q₁) is preferably not more than 120° C., especially notmore than 90° C.

Less than 1×10³ or more than 2×10⁴ of the weight-average molecularweight results in lowering of the electrostatic property, and hence, theeffect of the present invention can not be attained.

Macromonomer (M_(C)) for the polymer (Q₁) contains at least one polargroup in an amount of 0.5 to 15% by weight, preferably 1 to 10% byweight based on the total weight of the polymer (Q₁).

Less than 0.5% by weight of the polar group results in lower initialpotential which causes insufficient density of images, and more than 15%by weight results in poor dispersion properties which causesdeterioration of image quality and background contamination, even if thepolymer (Q₁) has a low molecular weight.

The polymer segment corresponding to the repeating unit of the formula(I) may be contained in an amount of not less than 30% by weight,preferably 50 to 97% by weight and the macromonomer (M_(C)) may becontained in an amount of 3 to 50% by weight, preferably 3 to 40% byweight based on the total weight of the polymer (Q₁).

Less than 30 by weight of the polymer segment or less than 30 by weightor more than 50% by weight of the macromonomer (M_(C)) results inlowering of the electrostatic property (in particular, dark chargeretention property and photosensitivity), and results in slightly higherfrequency in changes of dark charge retention property andphotosensitivity under a severe condition such as high or lowtemperature and high or low humidity, especially in anelectrophotographic material using a dye which spectrally sensitizes innear infrared to infrared region of wavelength, and hence, the effect ofthe present invention, that is a stable image reproduction, can not beattained sufficiently.

The following illustrates the monomer represented by the formula (I)which may be contained in an amount of not less than 30% by weight inpolymer (Q₁).

In the formula (I), preferably b¹ and b² each represents independently ahydrogen atom, a halogen atom (such as chlorine atom and bromine atom),a cyano group, an alkyl group having 1 to 4 carbon atoms (such asmethyl, ethyl, propyl and butyl), --COOZ⁴ or --Z² --COOZ⁴ (Z⁴ is ahydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenylgroup having 2 to 18 carbon atoms, an aralkyl group having 7 to 18carbon atoms, an alicyclic group having 3 to 18 carbon atoms or an arylgroup having 6 to 18 carbon atoms which may be substituted such asgroups exemplified below for R³, and Z² is a hydrocarbon group).

R³ is preferably an alkyl group having 1 to 18 carbon atoms which may besubstituted (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl,decyl, dodecyl, tridecyl, tetradecyl, 2-chloroethyl, 2-bromoethyl,2-cyanoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl and3-hydroxypropyl), an alkenyl group having 2 to 18 carbon atoms which maybe substituted (such as vinyl, allyl, isopropenyl, butenyl, hexenyl,heptenyl and octenyl), an aralkyl group having 7 to 12 carbon atomswhich may be substituted (such as benzyl, phenethyl, naphthylmethyl,2-naphthylethyl, methoxybenzyl, ethoxybenzyl and methylbenzyl), acycloalkyl group having 5 to 8 carbon atoms which may be substituted(such as cyclopentyl, cyclohexyl and cycloheptyl) or an aryl group whichmay be substituted (such as phenyl, tolyl, xylyl, naphthyl,methoxyphenyl, ethoxyphenyl, fluorophenyl, difluorophenyl, bromophenyl,chlorophenyl, dichlorophenyl, iodophenyl, methoxycarbonylphenyl,ethoxycarbonylphenyl and cyanophenyl).

Among the monomers represented by the formula (I), those correspond tothe units represented by the following formulae (Ia) and (Ib) are morepreferable: ##STR20##

Preferably, A¹ and A² in the formula (Ia), each represents independentlya hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon grouphaving 1 to 10 carbon atoms such as an alkyl group having 1 to 4 carbonatoms (for example, methyl, ethyl, propyl, butyl and the like), anaralkyl group having 7 to 9 carbon atoms (such as benzyl, phenethyl,3-phenylpropyl, chlorobenzyl, dichlorobenzyl, bromobenzyl, methylbenzyl,methoxybenzyl and chloromethylbenzyl), an aryl group (such as phenyl,tolyl, xylyl, bromophenyl, methoxyphenyl, chlorophenyl, dichlorophenyl),or --COR¹⁵ or --COOR¹⁵ (preferably, R¹⁵ represents a hydrocarbonsmentioned above as a hydrocarbon having 1 to 10 carbon atoms).

Preferably, B¹ and B² in the formulae (Ia) and (Ib) each representsindependently a single bond or a linking group having 1 to 4 atoms in amain chain such as --(CH₂)_(g) --(g is an integer of 1 to 3), --CH₂O--CO--, --CH₂ CH₂ O--CO--, --(CH₂ O)_(h) --(h is 1 or 2), especially asingle bond or a linking group having 1 to 2 atoms in a main chain.

The following is examples of the units represented by the formulae (Ia)and (Ib), which should not be understood to restrict the presentinvention. In the following formulae (a-1) to (a-20), c is an integer of1 to 4, d is integer of 0 or 1 to 3, e is an integer of 1 to 3, R¹⁶represents --C_(c) H_(2c+1) or --(CH₂)_(d) --C₆ H₅ (c and d are the sameas defined above), D¹ and D² are same or different, each represents ahydrogen atom, ---Cl, --Br or --I. ##STR21##

The following illustrates the monofunctional macromonomer (M_(C)) usedfor the polymer (Q₁).

The monofunctional macromonomer (M_(C)) has a weight-average molecularweight of not more than 1×10⁴ and contains one or more units having atleast one polar group selected from the group consisting of --PO₃ H₂,--SO₃ H, --COOH, --PO(OH)R¹ [R¹ is a hydrocarbon group or --OR₂ (R² is ahydrocarbon group)] and a residue of a cyclic anhydride-in its mainchain and a group having polymerizable double bond represented by theformula (II) in only one end of the main chain.

In the formula (II), V¹ represents --COO--, --OCO--, --CH₂ OCO--, --CH₂COO--, --O--, --SO₂ --, --CO--, --CONHCOO--, --CONHCONH--, --CONHSO₂ --,--CON(T¹)--, --SO₂ N(T¹)-- or --C₆ H₅ -- wherein T¹ represents ahydrogen atom or a hydrocarbon group.

Examples of a hydrocarbon group as T¹ include: a substituted orunsubstituted alkyl group having 1 to 18 carbon atoms (such as methyl,ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, hexadecyl,octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl,2-methoxycarbonylethyl, 2-methoxyethyl, 3-bromopropyl, an alkenyl grouphaving 4 to 18 carbon atoms which may be substituted (such as2-methyl-1-propenyl, 2,butenyl, 2-pentenyl, 3-methyl-2-pentenyl,1-pentenyl, 1-hexenyl, 2-hexenyl, 4-methyl-2-hexenyl), an aralkyl grouphaving 7 to 12 carbon atoms which may be substituted (such as benzyl,phenethyl, 3-phenylpropyl, naphtylmethyl, 2-naphtylethyl, chlorobenzyl,bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl,dimethoxybenzyl), an alicyclic group having 5 to 8 carbon atoms whichmay be substituted (cyclohexyl, 2-cyclohexylethyl, 2-cyclopentylethyl),an aromatic group having 6 to 12 carbon atoms which may be substituted(such as phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl,octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl,decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl,acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl,butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl,dodecyloylamidophenyl).

If V¹ is --C₆ H₄ --, the benzene ring may have substituent(s). Thesubstituents may be a halogen atom (such as a chlorine and bromineatom), an alkyl group (such as methyl, ethyl, propyl, butyl,chloromethyl and methoxymethyl) or an alkoxy group (such as methoxy,ethoxy, propoxy, butoxy).

Preferably, b³ and b⁴ each represents independently a hydrogen atom, ahalogen atom (such as a chlorine atom and a bromine atom), a cyanogroup, an alkyl group having 1 to 4 carbon atoms (such as methyl, ethyl,propyl and butyl), --COOZ¹ or --Z² --COOZ¹ (z¹ is a hydrogen atom or analkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an alicyclicgroup having 3 to 18 carbon atoms or an aryl group having 6 to 18 carbonatoms which may be substituted such as groups exemplified above for T¹,and Z² is the same as defined above).

Preferably, Z² may be methylene, ethylene, or propylene.

Especially, in the formula (II), V¹ may be ---COO--, --OCO--, --CH₂COO--, --CH₂ COO--, --O--, --CONHCOO--, --CONHCONH--, --CONH--, --SO₂NH-- or --CH₆ H₅ -- and b³ and b⁴ may be same or different, eachrepresents a hydrogen atom, methyl group, --COOZ¹ or --CH₂ COOZ¹ [Z¹ isa hydrogen atom or an alkyl group having 1 to 6 carbon atoms (such asmethyl, ethyl, propyl, butyl, hexyl)]. More preferably, one of b³ and b⁴may be a hydrogen atom.

Examples of groups having the polymerizable double bond include CH₂═CHCO--, CH₂ ═C(CH₃)COO--, CH(CH₃)═CHCOO--, CH₂ ═C(CH₂ COOCH₃)COO--, CH₂═C(CH₂ COOH)COO--, CH₂ ═CHCONH--, CH₂ ═C(CH₃)--CONH--, C(CH₃)H═CHCONH--,CH₂ ═CHOCO--, CH₂ ═CHCH₂ OCO--, CH₂ ═CHO--, CH₂ ═C(COOH)CH₂ COO--, CH₂═(COOCH₃)CH₂ COO--, CH₂ ═C(CH₃)CONHCOO--, CH₂ ═(CH₃)CONHCONH--, CH₂═CHC₆ H₄ --.

The macromonomer (M_(C)) contains an addition-copolymerizable unithaving at least one polar group selected from the group consisting of--PO₃ H₂, --SO₃ H, --COOH, --OH, --CHO, --PO(OH)R¹ and a residue of acyclic anhydride.

In the formula --PO(OH)R¹, R¹ represents a hydrocarbon group or --OR²(R² represents a hydrocarbon group). Examples of R¹ include an aliphaticgroup having 1 to 22 carbon atoms which may be substituted (such asmethyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl,2-chloroethyl, 2-methoxyethyl, 3-ethoxypropyl, allyl, crotonyl, butenyland cyclohexyl), an aralkyl group having 7 to 22 carbon atoms which maybe substituted (such as benzyl, phenethyl, 3-phenylpropyl, methylbenzyl,chlorobenzyl, fluorobenzyl, methoxybenzyl), or an aryl group having 6 to22 carbon atoms which may be substituted (such as phenyl, tolyl,ethylphenyl, propylphenyl, chlorophenyl, fluorophenyl, bromophenyl,chloromethylphenyl, dichlorophenyl, methoxyphenyl, cyanophenyl,acetamidophenyl, acetylphenyl and butoxyphenyl). Examples of R² are thesame as exemplified for R¹.

The residue of a cyclic anhydride may be a residue of an aliphaticdicarboxylic anhydride or a residue of an aromatic dicarboxylicanhydride.

Examples of aliphatic dicarboxylic anhydride include: succinicanhydride, glutaconic anhydride, maleic anhydride,cyclopentane-1,2-dicarbonic anhydride, cyclohexane-1,2-dicarboxylicanhydride and 2,3-bicyclo[2,2,2]octadicarboxylic anhydride, which may besubstituted, for example, by a halogen atom such as a chlorine atom anda bromine atom or an alkyl group such as methyl, ethyl, butyl and hexyl.

Examples of aromatic dicarboxylic anhydride include: cyclic phthalicanhydride, cyclic naphthalene dicarboxylic anhydride, pyridinedicarboxylic anhydride, thiophene, dicarboxylic anhydride, these cyclicanhydrides may be substituted, for example, by a halogen atom such as achlorine atom and a bromine atom or an alkyl group such as methyl,ethyl, propyl and butyl, a hydroxyl group, a cyano group, a nitro group,alkoxy carbonyl group (alkoxy may be methoxy, ethoxy and the like).

The above mentioned units may be any units corresponding to vinyliccompounds having polar group(s) which can be copolymerized with otherpolymerizable component(s). The vinylic compounds are described in, forexample, Polymer Society of Japan, "Polymer data handbook(fundamentals)" published by Baifukan, (1986). Examples of the compoundsinclude acrylic acids, α and/or β-substituted acrylic acid (such asα-acetoxy acrylic acid, α-acetoxymethyl acrylic acid, α- (2-amino)ethylacrylic acid, α-chloro acrylic acid, α-bromo acrylic acid, α-fluoroacrylic acid, α-tributylsylil acrylic acid, α-cyano acrylic acid,β-chloro acrylic acid, β-bromo acrylic acid, α-chloro-β-methoxy andα,β-dichloro acrylic acid), methacrylic acid, itaconic acid, semi esterof itaconic acid, semi amides of itaconic acid, crotonic acid,2-alkenylcarboxylic acids (such as 2-pentenoic acid, 2-methyl-2-hexenoicacid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoicacid), maleic acid, semi esters of maleic acid, semi amides of maleicacid, vinyl benzene carboxylic acid, vinyl benzene sulfonic acid, vinylsulfonic acid, vinyl phosphonic acid, vinyl- or allyl-semi ester ofdicarboxylic acids, and esters and amides of these carboxylic acids andsulfonic acids, which contain polar group(s) as substituent(s).

Examples of the unit having polar group(s) are as follows: ##STR22##wherein b¹ is --H or --CH₃ ; b² is --H, --CH₃ or --CH₂ COOCH₃ ; R¹⁷ isan alkyl group having 1 to 4 carbon atoms; R¹⁸ is an alkyl group having1 to 6 carbon atoms, benzyl or phenyl; f is an integer of 1 to 3, g isan integer of 2 to 11, h is an integer of 1 to 11, i is an integer of 2to 4 and j is an integer of 2 to 10.

The macromonomer (M_(C)) of the present invention may contain other unittogether with the unit having the polar group(s) mentioned above.

The units includes the unit corresponding to the monomer represented bythe following formula (VI): ##STR23##

In the formula (VI), V⁴ represents --CQO--, --OCO--, --(CH₂)_(m) OCO--,--(CH₂)_(m) COO-- (m is an integer of 1 to 3), --O--, --SO₂ --, --CO--,--CON(T¹)--, --SO₂ N(T¹)--, --CONHCOO--, --CONHCONH-- or --C₆ H₅ --wherein T¹ has the same meaning as defined above.

R¹⁹ represents a hydrocarbon group, provided that R¹⁹ represents ahydrogen atom or a hydrocarbon group when V⁴ is --C₆ H₄ --. Thehydrocarbon group is preferably an alkyl group having 1 to 22 carbonatoms which may be substituted (such as methyl, ethyl., propyl, butyl,hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl,octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl,2-methoxycarbonylethyl, 2-methoxyethyl and 3-bromopropyl), an alkenylgroup having 4 to 18 carbon atoms which may be substituted (such as2-methyl-1-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl,1-pentenyl, 1-hexenyl, 2-hexenyl and 4-methyl-2-hexenyl), an aralkylgroup having 7 to 12 carbon atoms which may be substituted (such asbenzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl,chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl,dimethylbenzyl and dimethoxybenzyl), a cycloalkyl group having 5 to 8carbon atoms which may be substituted (such as cyclohexyl,2-cyclohexylethyl and 2-cyclopentylethyl) or an aryl group having 6 to12 carbon atoms which may be substituted (such as phenyl, naphthyl,tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl,methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl,dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl,methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl,acetamidophenyl, propioamidophenyl, dodecyloylamidophenyl).

If V⁴ is --C₆ H₄ --, the benzene ring may have substituent(s). Thesubstituents may be a halogen atom (such as a-chlorine and bromineatom), an alkyl group (such as methyl, ethyl, propyl, butyl,chloromethyl and methoxymethyl) or an alkoxy group (such as methoxy,ethoxy, propoxy, butoxy).

b⁷ and b⁸ may be same or different, preferably each representsindependently a hydrogen atom, a halogen atom (such as chlorine atom andbromine atom), a cyano group, an alkyl group having 1 to 4 carbon atoms(such as methyl, ethyl, propyl and butyl), --COOZ⁵ or --Z² --COOZ⁵ (Z⁵is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, analkenyl group having 2 to 18 carbon atoms, an aralkyl group having 7 to18 carbon atoms, an alicyclic group having 3 to 18 carbon atoms or anaryl group having 6 to 18 carbon atoms which may be substituted such asgroups exemplified above for T¹, and Z² has the same meaning as definedabove).

Preferably, Z² may be methylene, ethylene, or propylene.

Especially, in the formula (IV), V⁴ may be --COO--, --OCO--, --CH₂OCO--, --CH₂ COO--, --O--, --CONH--, --SO₂ NH-- or --C₆ H₅ -- and b⁷ andb⁸ may be same or different, each represents a hydrogen atom, methylgroup, --COOZ⁵ or --CH₂ COOZ⁵ [Z⁵ is a hydrogen atom or an alkyl grouphaving 1 to 6 carbon atoms (such as methyl, ethyl, propyl, butyl,hexyl)]. More preferably, one of b⁷ and b⁸ may be a hydrogen atom.

These units may be contained in the macromonomer (M_(C)) in an amount of50 to 99% by weight, preferably 70 to 95% by weight based on the totalweight of the units contained in the macromonomer (M_(C)). Less than 50%and more than 99% by weight of the unit result in lowering of theelectrostatic property.

The macromonomer (M_(C)) can further contain other unit(s).

Examples of other units include: a residue of methacrylic acid esters,acrylic acid esters and crotonic acid esters having a group(s) otherthan groups mentioned above for the substituent group in the formula(I); a residue of α-olefins; a residue of vinyl or allyl carboxylate(carboxylic acid may be acetic acid, propionic acid, butyric acid,valeric acid, benzoic acid and naphthalene carboxylic acid); a residueof acrylonitrile; a residue of methacrylonitrile; a residue of vinylethers; a residue of itaconic acid esters (such as dimethyl esters anddiethyl esters); a residue of acrylamides; a residue of methacrylamides;a residue of styrenes (such as styrene, vinyl toluene, chlorostyrene,hydroxystyrene, N,N-dimethylaminomethylstyrene, methoxycarbonylstyrene,methanesulfonyloxystyrene and vinylnaphthalene); a residue of a compoundhaving vinyl sulfone group; a residue of a compound having vinyl ketonegroup; a residue of a heterocyclic compound having a vinyl group (suchas vinyl pyrrolidone, vinyl pyridine, vinyl imidazole, vinyl thiophene,vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyltetrazole and vinyloxazine). The above other units may preferably becontained in an amount of less than 20% by weight based on the totalweight of the units constituting the polymer chain.

(The polymer (Q₂))

As explained above, weight-average molecular weight of the polymer (Q₂)is 1×10³ to 2×10⁴, preferably 3×10³ to 1×10⁴ and glass transitiontemperature of the polymer (Q₂) is preferably -40° C. to 110° C.,especially -20° C. to 90° C.

Less than 1×10³ of the weight-average molecular weight result in lowerability of coating which causes insufficient film strength. On the otherhand, more than 2×10⁴ of the weight-average molecular weight result inslightly higher frequency in change of electrophotographic propertiessuch as dark charge retention property and initial potential under asevere condition such as high or low temperature and high or lowhumidity, especially in an electrophotographic material using a dyewhich spectrally sensitizes in near infrared to infrared region ofwavelength, and hence, the effect of the present invention, that is astable image reproduction, can not be attained sufficiently.

In the polymer (Q₂) of the present invention, the ratio by weight of themacromonomer (M_(D)) to other monomer (e.g. the monomer represented bythe formula (VII) shown below) ranges from 1-60 to 99-40, preferablyfrom 5-40 to 95-60.

Less than 1.0% by weight of the macromonomer in the polymer (Q₂) resultsin lower electrophotographic properties such as dark charge retentionproperty and photosensitivity, and results in higher frequency in changeof the electrophotographic properties under various environmentalcondition, especially when dye spectrally sensitizing in near infraredto infrared region of wavelength is used. This appears to be due to thefact that the polymer (Q₂) becomes almost the same as a conventionalhomopolymer or rondam copolymer, when the macromonomer (M_(D)) necessaryto form the graftcopolymer is used in so small amount. On the otherhand, more than 60% by weight of the macromonomer in the polymer (Q₂)results in insufficient copolymerizability between the macromonomer(M_(D)) and monomer(s) corresponding to other unit(s) which causesinsufficient properties as a binder.

Macromonomer (M_(D)) for the polymer (Q₂) preferably contains at leastone polar group in an amount of 1 to 20% by weight, more preferably 3 to15% by weight based on the total weight of the polymer (Q₂). Amount ofthe polar group in the polymer (Q₂) can be controlled by varying ratioof A block to B block in the macromonomer (M_(D)) or ratio of themacromonomer (M_(D)) per se in the polymer (Q₂).

Less than 1% by weight of the polar group results in lowering of initialpotential which causes insufficient density of images, and more than 20%by weight results in poor dispersion properties which causesdeterioration of image quality and background contamination when used asoffset master, even if the polymer (Q₂) has a low molecular weight.

The following illustrates the one-functional macromonomer (M_(D)) forthe graft type copolymer of the present invention in detail.

As described above, copolymer segment in the macromonomer (M_(D)) iscomposed of A and B blocks. The ratio by weight of A block to B blockmay be 1-70 to 99-30, preferably 3-50 to 97-50.

A block of the macromonomer (M_(D)) contains at least one unit having atleast one polar group selected from the group consisting of --PO₃ H₂,--SO₃ H, --COOH, phenolic hydroxyl group, --PO(OH)R¹ wherein R¹ is ahydrocarbon group or --OR² (R² is a hydrocarbon group) and a residue ofa cyclic anhydride. --COOH, --SO₃ H, phenolic hydroxyl group and--PO(OH)R¹ are preferable.

R¹ represents a hydrocarbon group or --OR² (R² is a hydrocarbon group),preferably R¹ and R² each represents independently an aliphatic grouphaving 1 to 22 carbon atoms which may be substituted (such as methyl,ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl,2-chloroethyl, 2-methoxyethyl, 3-ethoxypropyl, allyl, crotonyl, butenyl,cyclohexyl and the like); an aralkyl group having 7 to 22 carbon atomswhich may be substituted (such as benzyl, phenethyl, 3-phenylpropyl,methylbenzyl, chlorobenzyl, fluorobenzyl, methoxybenzyl and the like);an aryl group having 6 to 22 carbon atoms which may be substituted (suchas phenyl, tolyl, ethylphenyl, propylphenyl, chlorophenyl, fluorophenyl,bromophenyl, chloro-methylphenyl, dichlorophenyl, methoxyphenyl,cyanophenyl, acetamidephenyl, acetylphenyl, butoxyphenyl and the like).

Examples for the residue of a cyclic anhydride are the same asexemplified in the explanation for the polymer (Q₁).

The above mentioned unit may be any unit corresponding to vinyliccompound having polar group(s) which can be copolymerized with an unitconstituting other block, that is, a vinylic compound corresponding topolymethacrylate segment represented by the formula (III).

The vinylic compounds are described in, for example, Polymer Society ofJapan, "Polymer data handbook (fundamentals)" published by Baifukan,(1986). Examples of the compounds include acrylic acids, α and/or,β-substituted acrylic acid (such as α-acetoxy acrylic acid,α-acetoxymethyl acrylic acid, α-(2-amino)ethyl acrylic acid, α-chloroacrylic acid, α-bromo acrylic acid, α-fluoro acrylic acid,α-tributylsylil acrylic acid, α-cyano acrylic acid, β-chloro acrylicacid, β-bromo acrylic acid, α-chloro-β-methoxy and α,β-dichloro acrylicacid), methacrylic acid, itaconic acid, semi ester of itaconic acid,semi amides of itaconic acid, crotonic acid, 2-alkenylcarboxylic acids(such as 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid,4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid), maleic acid, semiesters of maleic acid, semi amides of maleic acid, vinyl benzenecarboxylic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid, vinylphosphonic acid, vinyl- or allyl-semi ester of dicarboxylic acids, andesters and amides of these carboxylic acids and sulfonic acids, whichcontain polar group(s) as substituent(s).

Examples of the compounds having polar group(S) are as follows:##STR24## wherein p¹ is --H, --CH₃, --Cl, --Br, --CN, --CH₂ COOCH₃ or--CH₂ COOH; p² is --H or --CH₃ ; b is an integer of 2 to 18, c is aninteger of 1 to 12 and d is an integer of 1 to 4.

As shown above, the unit may contain more than two kinds of polar groupin A block and the unit containing polar group may be present in A blockas an unit of either random copolymer or block copolymer. Further, Ablock may contain other unit having no polar group (for example, theunit represented by formula (III)) together with the unit having thepolar group mentioned above. The unit having the polar group may becontained in A block in an amount of 30 to 100% by weight based on thetotal weight of A block.

The following illustrates an unit constituting B block in themacromonomer (M_(D)), that is, an unit represented by the formula (III).

In the formula (III), V² represents --COO--, --OCO--, --(CH₂)_(a) OCO--,--(CH₂)_(a) COO-- (a is an integer of 1 to 3), --O--, --SO₂ --, --CO--,--CON(T¹)--, --SO₂ N(T¹)--, --CONHCOO--, --CONHCONH-- or --C₆ H₅ --wherein T¹ has the same meaning as defined in formula (II) and examplesfor T¹ are the same as exemplified in the explanation for V¹ in theformula (II).

R⁴ represents a hydrocarbon group, preferably those exemplified for T¹as preferable hydrocarbon groups.

If V² is --C₆ H₄ --, R⁴ represents a hydrocarbon group and a hydrogenatom and the benzene ring may have substituent(s). The substituents maybe a halogen atom (such as a chlorine and bromine atom), an alkyl group(such as methyl, ethyl, propyl, butyl, chloromethyl and methoxymethyl)or an alkoxy group (such as methoxy, ethoxy, propoxy, butoxy).

Preferably, b⁵ and b⁶ are same or different, each representsindependently a hydrogen atom, a halogen atom (such as chlorine atom andbromine atom), a cyano group, an alkyl group having 1 to 4 carbon atoms(such as methyl, ethyl, propyl and butyl), --COOZ⁵ or --Z² --COOZ⁵ (Z⁵is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, analkenyl group having 2 to 18 carbon atoms, an aralkyl group having 7 to18 carbon atoms, an alicyclic group having 3 to 18 carbon atoms or anaryl group having 6 to 18 carbon atoms which may be substituted such asgroups exemplified above for T¹, and Z² is a hydrocarbon group).

Preferably, Z² may be methylene, ethylene, or propylene.

Especially, in the formula (III), V² may be --COO--, --OCO--, --CH₂OCO--, --CH₂ COO--, --O--, --CONH--, --SO₂ NH-- or --C₆ H₅ -- and b⁵ andb⁶ may be same or different, each represents a hydrogen atom, methylgroup, --COOZ⁵ or --CH₂ COOZ⁵ [Z⁵ is preferably a hydrogen atom or analkyl group having 1 to 6 carbon atoms (such as methyl, ethyl, propyl,butyl, hexyl)]. More preferably, one of b⁵ and b⁶ may be a hydrogenatom.

Block B may contain other unit than the unit represented by the formula(III). Examples for monomer corresponding to the above other unitinclude acrylonitrile, methacrylonitrile and a heterocyclic compoundhaving a vinyl group (such as vinylpyridine, vinylimidazole,vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane andvinyloxazine). The above other units may preferably be contained in anamount of less than 20% by weight based on the total weight of block B.

It is preferable that block B contains no unit having polar group to becontained in block A. If block B contains not less than two units, thesemay be contained in B block as an unit of either random copolymer orblock copolymer. However, it is preferable to be contained as an unit ofrandom copolymer in view of simplicity of polymerization.

The following illustrates the unit having polymerizable double bondwhich links A block to B block to for. m A-B type linkage in themacromonomer (M_(D)) of the present invention, as well as the unithaving polymerizable double bond contained in the macromonomer (M_(D))at end of B block Chain opposite to the A-B linkage.

Specifically, the units having polymerizable double bond may berepresented by the following formula (VIII): ##STR25## wherein b⁵, b⁶and V² have the same meanings as defined for b⁵, b⁶ and V² in formula(III), respectively.

More specifically, examples of the units having polymerizable doublebond represented by the formula (VIII) include CH₂ ═CHCOO--, CH₂═C(CH₃)OCOO--, CH(CH₃)═CHCOO--, CH₂ ═C(CH₂ COOCH₃)COO--, CH₂ ═C(CH₂COOH)COO--, CH₂ ═CHCONH--, CH₂ ═C(CH₃)CONH--, CH(CH₃)═CHCONH--, CH₂═CHOCO--, CH₂ ═CHCH₂ OCO--, CH₂ ═CHO--, CH₂ ═C(COOH)CH₂ COO--, CH₂═C(COOCH₃)CH₂ COO--, CH₂ ═CHC₆ H₄ --, CH₂ ═CH(CH₂)₂ COO--, CH₂ ═CHCO--,CH₂ ═CH(CH₂)₂ OCO--.

The macromonomer (M_(D)) Of the present invention has a structure wherethe unit having polymerizable double bond represented by the formula(VIII) links to one end of B block chain directly or through an optionallinking group. Examples for the linking group include di-valent groupssuch as carbon-carbon, carbon-hetero atom (the hetero atom may be oxygenatom, sulfur atom, nitrogen atom and silicon atom), hetero atom-heteroatom linking group and combination thereof. Specific examples for thelinking group include --C(Z⁶)(Z⁶)-- [Z⁶ may be same or different, eachrepresent a hydrogen atom, a halogen atom (such as-fluorine atom,chlorine atom and bromine atom), a cyano group, a hydroxyl group or analkyl group (such as methyl, ethyl and propyl)], --CH═CH--, --C₆ H₁₀ --,--C₆ H₄ --, --O--, --S--, --CO--, --N(Z⁷)--, --COO--, --C(═S)--, --SO₂--, --CON(Z⁷)--, --SO₂ N(Z⁷)--, --NHCOO--, --NHCONH--, --C(Z⁷)(Z⁷)-- (Z⁷represents a hydrogen atom or a hydrocarbon group as exemplified for R⁴of formula (III)) and combination thereof.

More than 2×10⁴ of the weight-average molecular weight of themacromonomer (M_(D)) results in lower copolymerizability with othermonomer, for example, a monomer corresponding to the unit of the formula(VII) shown below. On the other hand, lower weight-average molecularweight of the macromonomer (M_(D)) results in reducing the improvementof electrophotographic properties in a photoconductive layer. Therefore,it is preferable that the weight-average molecular weight of themacromonomer (M_(D)) is not less than 1×10³.

The following is examples of the macromonomer (M_(D)) of the presentinvention, which should not be understood to restrict the presentinvention. In the following formulae (M-1) to (M-16), p³, p⁴ and p⁵ aresame or different, each is --H, --CH₃, or --CH₂ COOCH₃ ; p⁶ is --H or--CH₃ ; R²⁰ is --C_(p) H_(2p+1) (p is an integer of 1 to 18),--(CH₂)_(q) C₆ G₅ (q is an integer of 1 to 3), --C₆ H₄ --Y¹ (Y¹ is --H,--Cl, --Br, --CH₃, --OCH₃ or --COCH₃) or --(CH₂)_(r) --C₁₀ H₇ (r is aninteger of 1 to 3); R²¹ is --C_(s) H_(2s+1) (s is an integer of 1 to 8)or --(CH₂)_(q) C₆ H₅ ; Y² is --OH, --COOH, --SO₃ H, --OP(═O)(OH)₂ or--OP(═O)(OH)(OH)OCH₃ ; Y³ is --COOH, --SO₃ H, --OP(═O)(OH)₂ or--OP(═O)(OH)OCH₃ ; t is an integer of 2 to 12 and u is an integer of 2to 6. ##STR26##

In the polymer (Q₂), the monomer corresponding to the unit representedby the following formula (VII) is preferable for use in copolymerizationwith the macromonomer (M_(D)). ##STR27## wherein b⁹ and b¹⁰ eachrepresents independently a hydrogen atom, halogen atom, cyano group or ahydrocarbon group and R²² represents a hydrocarbon group.

Preferably, in the formula (VII) b⁹ and b¹⁰ each represents a hydrogenatom, halogen atom (such as a chlorine atom and a bromine atom), cyanogroup or a hydrocarbon group having 1 to 4 carbon atoms (such as methyl,ethyl, propyl, buthyl).

R²² represents a hydrocarbon group, specifically an alkyl, aralkyl groupor an aromatic ring, preferably an aralkyl group or an aromatic ringhaving benzene ring or naphthalene ring.

R²² is preferably a hydrocarbon group having 1 to 18 carbon atoms whichmay be substituted. The polymer chain constituted by the unitrepresented by the formula (VII) preferably contains no unit havingpolar group such as --PO₃ H₂, --SO₃ H, --COOH, --OH, --SH and --PO₃ R¹.Thus, the substituent group for R²² may be any group other than thepolar group contained in the unit contained in the polymer (Q₂), forexample, a halogen atom (such as a fluorine atom, a chlorine atom and abromine atom), --OZ⁶, --COOZ⁸, or --OCOZ⁸ (wherein Z⁸ represents ahydrocarbon group having 1 to 22 carbon atoms such as methyl, ethyl,propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl and octadecyl).Preferably, the hydrocarbon may be an alkyl group having 1 to 18 carbonatoms which may be substituted (such as methyl, ethyl, propyl, butyl,hexyl, heptyl, octyl, decyl, dodecyl, hexadecyl, octadecyl,2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl,2-methoxyethyl, 3-bromopropyl); an alkenyl group having 4 to 18 carbonatoms which may be substituted (such as-2-methyl-1-propenyl, 2-butenyl,2-pentenyl, 3-methyl-2-pentenyl, 1-pentenyl, 1-hexenyl, 2-hexenyl and4-methyl-2-hexenyl); an aralkyl group having 7 to 12 carbon atoms whichmay be substituted (such as benzyl, phenethyl, 3-phenylpropyl,naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl,methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl anddimethoxybenzyl); an alicyclic group having 5 to 8 carbon atoms whichmay be substituted (such as cyclohexyl, 2-cyclohexylethyl and2-cyclopentylethyl); or an aromatic group having 6 to 12 carbon atomswhich may be substituted (such as phenyl, naphthyl, tolyl, xylyl,propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl,ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl,dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl,methoxycarbonylphenyl, acetamidephenyl, propionamidephenyl anddodecyloylamidophenyl).

The units of the formula (VII) containing R²² is preferably themethacrylate unit represented by the following formulae (VIIa) and/or(VIIb) (hereinafter referred to as "polymer (QQ)"). ##STR28## whereinA^(1') and A^(2') each represents independently a hydrogen atom, ahydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, abromine atom, --COZ⁹ or --COOZ⁹ (Z⁹ represents a hydrocarbon grouphaving 1 to 10 carbon atoms) and B¹ and B² each represents independentlya single bond of a linking group having 1 to 4 atoms which links --COO--to benzene ring.

When the polymer (QQ) is used instead of the polymer (Q₂), an improvedelectrophotographic properties (especially, V₁₀, D.R.R., E_(1/10)) canbe obtained. Assumably, this would be due to appropriate arrangement,which is effected by the planar structure of benzene ring having thesubstituents at ortho position or unsubstituted naphthalene ring, of thepolymer chain at zinc oxide interface in the film.

In the formula (VIIa), preferably A^(1') and A^(2') each representsindependently a hydrogen atom, a chlorine atom, a bromine atom or ahydrocarbon group having 1 to 10 carbon atoms such as an alkyl grouphaving 1 to 4 carbon atoms (for example, ethyl, propyl and butyl), anaralkyl group having 7 to 9 carbon atoms (such as benzyl, phenethyl,3-phenylpropyl, chlorobenzyl, dichlorobenzyl, bromobenzyl, methylbenzyl,methoxybenzyl and chloromethylbenzyl), an aryl group (such as phenyl,tolyl, xylyl, bromophenyl, methoxyphenyl, chlorophenyl anddichlorophenyl), --COZ⁹ and --COOZ⁹ (preferably, Z⁹ represents ahydrocarbons mentioned above as a preferable hydrocarbon having 1 to 10carbon atoms).

In the formulae (VIIa) and (VIIb), preferably B¹ and B² each representsindependently a single bond or a linking group having 1 to 4 atoms,which links --COO-- to benzene ring, such as --(CH₂)_(e) -- (e is aninteger of 1 to 3), --CH₂ OCO--, --CH₂ CH₂ OCO--, --(CH₂)_(f) -- (f is 1or 2) and --CH₂ CH₂ O--, especially a single bond or a linking grouphaving 1 to 2 atoms.

The following is examples of the units represented by the formulae(VIIa) and (VIIb), which should not be understood to restrict thepresent invention. ##STR29##

In the graft type copolymer of the present invention, an unitcopolymerizable with the macromonomer (M_(D)) may be other than the unitrepresented by the formula (VII), (VIIa) or (VIIb).

Examples for the above other unit include a residue of methacrylic acidesters, acrylic acid esters and crotonic acid esters having a group(s)other than groups mentioned above for the substituent group in theformula (VII); a residue of α-olefins; a residue of vinyl or allylcarboxylate (carboxylic acid may be acetic acid, propionic acid, butyricacid, valeric acid, benzoic acid and naphthalene carboxylic acid); aresidue of acrylonitrile; a residue of methacrylonitrile; a residue ofvinyl ethers; a residue of itaconic acid esters (such as dimethyl estersand diethyl esters); a residue of acrylamides; a residue ofmethacrylamides; a residue of styrenes (such as styrene, vinyl toluene,chlorostyrene, hydroxystyrene, N,N-dimethylaminomethylstyrene,methoxycarbonylstyrene, methanesulfonyloxystyrene and vinylnaphthalene);a residue of a compound having vinyl sulfone group; a residue of acompound having vinyl ketone group; a residue of a heterocyclic compoundhaving a vinyl group (such as vinyl pyrrolidone, vinyl pyridine, vinylimidazole, vinyl thiophene, vinyl imidazoline, vinyl pyrazole, vinyldioxane, vinyl quinoline, vinyl tetrazole and vinyloxazine), preferablya residue of vinyl or allyl carboxylates having 1 to 3 carbon atoms, aresidue of acrylonitrile, a residue of methacrylonitrile, a residue ofstyrenes (such as styrene, vinyltoluene, butylstyrene, methoxystyrene,chlorostyrene, dichlorostyrene, bromostyrene and ethoxystyrene).

(Preparation of the polymer (Q))

The following illustrates a method for preparing the polymer (Q), thatis the polymers (Q₁) and (Q₂), and the one-functional macromonomers(M_(C)) and (M_(D)) for the polymers (Q₁) and (Q₂).

The polymer (Q) or the one-functional macromonomer (M_(C)) or (M_(D))may be prepared in accordance with known polymerization methods. Forexample, the macromonomer (M_(C)) or (M_(D)) may be prepared by themethod wherein the polar group in monomers corresponding to a particularunit is protected by a protective group, and the protective group isreleased through a hydrolysis, hydrogenation, oxidative degradation orphotodegradation after preparing a block copolymer by known livingpolymerization, reaction such as ionic polymerization by organic metalcompounds (such as alkyl lithiums, lithium diisopropylamide, alkylmagnesium halides) or hydrogen iodide/iodine or photopolymerizationwherein porphyrin metal complex is used as a catalyst or grouptransition polymerization. One example of the reactions is illustratedby the following reaction formulae (2) and (3). The reaction formula (2)is for the macromonomer (M_(C)) and the reaction formula (3) is for themacromonomer (M_(D)). ##STR30##

For example, the methods are described in the following literature: P.Lutz, P. Masson et al., Polym. Bull., 12, 79(1984) B. C. Anderson, G. D.Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute. etal., Polym. J. 17, 977 (1985), 18, 1037(1986), Koichi Migite, KoichiHatada, Kobunshikako, 36, 366(1987), Toshinobu Higashimura, MitsuoSawamoto, papers for Polymer, 46, 189 (1989), M. Kuroki, T. Aida, J. Am.Chem. Soc. 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Yukigoseikagaku,43, 300(1985), D. Y. Sogah, W. R. Hertler et al., Macromolecules, 20,1473(1987). A group having polymerizable double bond can be readilyintroduced to one end of the living polymer in accordance with knownmethod for preparing a macromonomer.

Specifically, the methods are described in the following literature: P.Dreyfuss & R. P. Quirk, Encycl. Polym. Sci. Eng., 7, 551 (1987), P. F.Rempp, E. Franta, Adv. Polym. Sci., 58, 1 (1984), V. Percec, Appl. Poly.Sci.,285, 95 (1984), R. Asami, M. Takari, Macromol. Chem. Suppl., 12,163 (1985), R. Rempp., et al, Macromol. Chem. Suppl., 8, 3 (1984), YushiKawakami, Chemical Industry, 38, 56 (1987), Yuya Yamashita, Polymer, 31,988 (1982), Shiro Kobayashi, Polymer, 30, 625 (1981), ToshinobuHigashimura, Journal of Japan Adhesive Society, 18, 536 (1982), KoichiIto, Polymer Processing, 35, 262 (1986), Shiro Toki, Takashi Tsuda,functional materials, 1987, No. 10, 5 etc.

Protection by the protective group and release of the protective groupcan be conducted easily by known techniques. Such methods are describedalso in the following references: Yoshio Iwakura, Keisuke Kurita,"Reactive Polymer", Kodansha Co.,Ltd. (1977), T. W. Green, "ProtectiveGroups in Organic Synthesis", John Wiley & Sons (1981), J. F. W. McOmie, "Protective Groups in Organic Chemistry" Plenum Press, (1973) etc.

Other methods for preparation of AB type block copolymer may be preparedby a photoinitiator polymerization method using a dithiocarbamatecompound as an initiator. The method is described in the followingliteratures: Takayuki Otsu, Polymer, 37, 248 (1988), Shunichi Hinoemori,Takaiti Otsu, Polym. Rep. Jap. 37, 3508 (1988), J. P. KOKAI Nos. Sho64-111 and Sho 64-26619 etc. The macromonomers (M_(C)) and (M_(D)) Ofthe present invention can be obtained by combining these method and theabove mentioned macromonomer preparation method.

The polymer (Q) can be prepared by copolymerizing at least onemacromonomer mentioned above with at least one monomer, for example, themacromonomer (M_(C)) with the monomer of the formula (I) and themacromonomer (M_(D)) with the monomer of the formula (VII). Thepolymerization reaction can be carried out using a known polymerizationmethod such as solution polymerization, suspension polymerization,precipitation polymerization and emulsion polymerization. For example,when the solution polymerization is employed, the polymer (Q) can beobtained as a solution by copolymerizing a macromonomer with a monomerin a solvent such as benzene and toluene in the presence of a radicalinitiator such as azobis type compound and peroxide compound. Theresulting polymer (Q) is obtained as a solid through drying orreprecipitation. On the other hand, when the suspension polymerizationis employed, the polymer (Q) can be obtained by suspending amacromonomer and a monomer in the presence of a dispersant such aspolyvinylalcohol and polyvinylpyrrolidone and then copolymerizing themin the presence of a radical initiator.

(The polymer (R))

The following illustrates the polymer (R) containing at least one photoand/or thermosetting group.

The photo and/or thermosetting group may be any group. However, forexample, the groups mentioned above for the polymer (P) may becontained.

The polymer (R) may be any known polymer having the photo and/orthermosetting group used for the electrophotographic materials.

The polymer may be those described in the following literature: TakaharuShibata, Jiro Isiwatari, Polymer, 17, p.278 (1968), Seiji Miyamoto,Hidehiko Takei, Imaging, 1973, (No.8), Koich Nakamura, "PracticalTechniques or Binder for Recording Materials", Chapter 10, C.H.CCo.,Ltd.,(1985), "Denshishasinyo yukikankotai no genjo sinpojium,Yokoshu" (1985), Hiroshi Kokado, "Recent Development and Utilization ofPhotoconductive Material and Photosensitive Material", published byNihonkagakujoho Co.,Ltd.,(1986), Denshishashingakkai,"Denshishashingijutu no kiso to oyo" the chapter 5, Korona sha, (1988),D. Tatt, S. C. Heidecker, Tappi,49, (No. 10), 439 (1966), E. S.Baltazzi, R. G. Blanclotte et al, Phot. Sci. Eng. 16, (No.5), 354(1972), Guen Chan Kei, Isamu Shimizu, Eiichi Inoue, Journal of Societyof Electrophotographics of Japan,18, (No. 2), 22, (1980).

Examples of the polymer (R) include: olefin polymer and copolymer, vinylchloride copolymer, vinylidene chloride copolymer, vinyl alkanoatepolymer and copolymer, allyl alkanoate polymer and copolymer, polymerand copolymer of styrene or derivative thereof, butadiene-styrenecopolymer, isoprene-styrene copolymer, butadiene-unsaturated carboxylatecopolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkylvinyl ether copolymer, acrylate polymer and copolymer, methacrylatepolymer and copolymer, styrene-acrylate copolymer, styrene-methacrylatecopolymer, itaconic acid diester polymer and copolymer, maleic anhydridecopolymer, acrylamide copolymer, methacrylamide copolymer, hydroxymodified silicone resin, polycarbonate resin, ketone resin, polyesterresin, silicone resin, amide resin, hydroxy- and carboxyl-modifiedpolyester resin, butyral resin, polyvinylacetal resin, cyclizedrubber-methacrylate copolymer, cyclized rubber-acrylic ester copolymer,copolymer having heterocycle which does not have a nitrogen atom(heterocycle may be furan, tetrahydrofuran, thiophene, dioxane,dioxofuran, lactone, benzofuran, benzothiophene and 1,3-dioxetane) andepoxy resins.

Unit containing at least one photo and/or thermosetting group may becontained in the polymer (R) in an amount of 0.1-40% by weight,preferably 1-30% by weight based on the total weight of the polymer (R).

Less than 0.1% by weight of the unit results in insufficient improvementin hardening coating which causes disadvantageous influence onreleasability of the transfer layer.

On the other hand, more than 40% by weight of the unit results in lowerelectrophotographic properties as a binder resine of the photoconductivelayer which causes lower reproducibility of duplicated image andbackground contamination.

Preferably, the polymer (R) containing the photo and/or thermosettinggroup may be contained in the whole binder resine in an amount of notless than 40% by weight based on the total weight of the binder resine,since less than 40% by weight of the unit results in insufficientimprovement in hardening coating which causes disadvantageous influenceon releasability of the transfer layer.

On the other hand, more than 40% by weight of the polymer (R) results inlower electrophotographic properties.

A photo and/or thermosetting resin may be any known curable resins, forexample, resins having curable groups explained above for the segment(Y) of the polymer (P).

In the photoconductive layer of the present invention, other binderresins can be employed in addition to the polymer (P), the polymer (Q)and the polymer (R). Such other resins may be any resins used in knownelectrophotographic materials as mentioned with respect to the polymer(R).

(Photo and/or thermosetting agent)

Preferably, the photoconductive layer of the electrophotographicmaterial for ,color proofing of the present invention may furtherinclude a small amount of photo and/or thermosetting agent in order toimprove curing characteristics of the coating. The word "photo and/orthermosetting agent" means a photo and/or thermosetting compound,oligomer, and resin and a crosslinking agent in this specification.

The photo and/or thermosetting agent may be used in an amount of 0.01-20parts by weight, preferably 0.1-15 parts by weight per 100 parts byweight of the total amount of the polymer (P), the polymer (Q) and thepolymer (R).

Less than 0.01 parts by weight of the photo and/or thermosetting agentresults in insufficient improvement in hardening coating. More than 20parts by weight of the photo and/or thermosetting agent results indisadvantageous influence on an electrophotographic property.

A photo and/or thermosetting resin may be any known curable resins, forexample, resins having curable groups explained above for the segment(Y) of the polymer (P).

The photo and/or thermosetting agent may be a crosslinking agent whichis generally used as a crosslinking agent in the art and disclosed inthe following literatures: Shinzo Yamamoto, Tosuke Kaneko, "Crosslinking agent handbook", published by Taiseisha (1981); Kobunshigakkai,"Polymer Data Handbook (Fundamentals)", Baifukan (1986).

Examples of crosslinking agents include: organic silane compounds (suchas silane coupling agent of vinyl trimethoxy silane, vinyl tributoxysilane, γ-glycidoxy propyl trimethoxy silane, γ-mercapto propyltriethoxy silane, γ-aminopropyltriethoxy silane), polyisocyanatecompounds (such as toluylene diisocyanate, o-toluylene diisocyanate,diphenylmethane diisocyanate, triphenylmethane triisocyanate,polymethylenepolyphenyl isocyanate, hexamethylene diisocyanate,isophorone diisocyanate, polymeric polyisocyanate), polyols (such as1,4-butanediol, polyoxypropyleneglycol, polyoxyalkyleneglycol,1,1,1-trimthylolpropane), polyamines (such as ethylenediamine, γ-hydroxypropyl ethylenediamine, phenylene diamine, hexamethylene diamine,N-aminoethylpiperazine, modified aliphatic polyamine), polyepoxy groupcontaining compounds and epoxy resins (such as compounds described inHiroshi Kakiuchi, "Novel Epoxy Resins", Shokodo, (1985), KuniyukiHashimoto, "Epoxy Resins", Nikkan kogyo newspaper company,(1969)),melamine resins (such as compounds described in Mitsuwa Ichiro, HideoMatsunaga, "Urea Melamine Resins", Nikkan kogyo newspaper company,(1969)) and poly(metha)acrylate compound (such as compound described inHaranobu Okawa, Takeo Saegusa, Toshinobu Higasimura, "Oligomer",Kodansha, (1976), Eizo Omori, "Functional acrylic resin", Technosystem,(1985)). Further, monomers having polyfunctional curable groups such asvinylmethacrylate, allylmethacrylate, ethyleneglycoldiacrylate,polyethyleneglycoldiacrylate, divinylsuccinate, divinyladipate,diallylsuccinate, 2-methylvinylmethacrylate,trimethylolpropanetrimethacrylate, divinylbenzene and pentaerythrytolpolyacrylate may also be used.

As explained above, the present invention is characterized in that thephotoconductive layer which contacts with a transfer layer is curedafter-the photoconductive layer is formed by coating. Accordingly, it ispreferable to use the polymer (P), the polymer (Q), the polymer (R), andthe photo and/or thermosetting agent in appropriate combination so thateach polymer may have functional groups which can bond chemically witheach other.

Such combinations of functional groups are well known in the art Forexample, the combinations of functional groups are shown in Table 1 ascombination of functional groups of Group A and functional groups ofGroup B. The table should not be understood to limit the presentinvention.

                  TABLE 1                                                         ______________________________________                                        Group A Group B                                                               ______________________________________                                        COOH                                                                                   ##STR31##                                                            PO.sub.3 H.sub.2                                                                      COCl, SO.sub.2 Cl, a residue of a cyclic anhydride                    OH      NCO, NCS,                                                             SH NH.sub.2                                                                            ##STR32##                                                            NHR SO.sub.2 H                                                                         ##STR33##                                                                    a block isocyanate group                                                       ##STR34##                                                                     ##STR35##                                                                     ##STR36##                                                            ______________________________________                                    

In the Table 1, R represents a hydrocarbon group, R¹⁵ and R¹⁶ eachrepresents an alkyl group and R¹⁷ to R¹⁹ each represents an alkyl oralkoxy group, provided that at least one of R¹⁷ to R¹⁹ is an alkoxygroup. B¹ and B² each represents an electron attractive group such as--CN, --CF₃, --COR²⁰, --COOR²⁰ and --SO₂ OR²⁰ (R²⁰ is a hydrocarbongroup such as C_(n) H_(2n+1) (n is an integer of 1 to 4), --CH₂ C₆ H₅and --C₆ H₅).

(Other additives)

A reaction accelerator may optionally be added to the binder (Q) inorder to promote crosslinking reaction.

If the crosslinking reaction is a reaction of forming chemical bondsbetween functional groups, the following accelerator may be used:organic acids (such as acetic acid, propionic acid, butyric acid,benzensulfonic acid and p-toluenesulfonic acid); phenols (phenol,chlorophenol, nitrophenol, cyanophenol, bromophenol, naphthol anddichlorophenol), organometallic compounds (such as zirconiumacetylacetonate, zirconium acetylacetate, cobalt acetyl acetate and tindibutoxy dilaurylate), dithiocarbamic acid compounds (such as salts ofdiethyldithiocarbamic acid), thiuram disulfide compounds (such astetramethylthiuram disulfide) and carboxylic anhydrides (such asphthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinicanhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride andtrimellitic anhydride).

If the crosslinking reaction is a polymerization reaction, apolymerization initiator (such as peroxides and azobis compounds) may beused.

The above mentioned binder is cured by light and/or heat after coating.Cure by heat requires severer drying condition than the conditionrequired for preparation of conventional electrophotographic materials.For example, higher temperature and/or longer time period are requiredfor drying. Alternatively, it is preferable to heat the binder afterdrying a coating solvent. Heating may be conducted in the temperaturebetween 60° C. and 150° C. , for 5 to 120 minutes. Milder condition ispossible if the above mentioned reaction accelerator is used.

Methods of photo-setting of particular functional groups of the resin ofthe present invention may be conducted with an actinic radiation.

The actinic radiation may be visible light, ultraviolet light, farultraviolet light, electron beams, X rays, γ rays, α rays, preferablyultraviolet. Rays having wave length between 310 nm and 500 nm isespecially preferable. Generally, a mercury vapor lamp, a halogen lamp,etc. are used for the radiation. The radiation may be conducted at thedistance of 5-50 cm, for the period of 10 seconds to 10 minutes.

(Photoconductive compounds)

The photoconductive compound used in the present invention may be eitherorganic compounds or inorganic compounds.

The compound may be, for example, a known inorganic photoconductivecompound such as zinc oxide, titanium oxide, zinc sulfide, cadmiumsulfide and lead sulfide. Zinc oxide and titanium oxide are preferablefrom the environmental point of view.

If an inorganic photoconductive compound such as zinc oxide and titaniumoxide are used, the binder resins are used in an amount of 10-100 byweight, preferably 15 to 40 parts by weight based on 100 parts by weightof the inorganic compound.

Organic photoconductive compounds may be any known compounds. Forexample, there may be mentioned those used in photoconductive layercomprising an organic photoconductive compound, a sensitizing dye and abinder resin described in J.P. KOKOKU Nos. Sho 37-17162 and Sho62-51462, J. P. KOKAI Nos. Sho 52-2437, Sho 54-19803, Sho 56-107246 andSho 57-161863; a photoconductive layer comprising a charge generatingagent, a charge transporting agent and a binder resin described in J. P.KOKAI Nos. Sho 56-146145, Sho 60-17751, Sho 60-17752, Sho 60-17760, Sho60-254142 and Sho 62-54266; a double layer type of photoconductive layercontaining a charge generating agent and a charge transporting agent indifferent layers described in J.P. KOKAI Nos. Sho 60-230147, Sho60-230148 and Sho 60-238853.

Examples of organic photoconductive compounds for the first typeinclude:

(a) Triazol derivatives described in U.S. Pat. No. 3,112,197;

(b) Oxadiazol derivatives described in U.S. Pat. No. 3,189,447;

(c) Imidazol derivatives described in J.P. KOKOKU No. Sho 37-16096;

(d) Polyarylalkane derivatives described in U.S. Pat. No. 3,615,402,U.S. Pat. No. 3,820,989, U.S. Pat. No. 3,542,544, J.P. KOKOKU No. Sho45-555 and Sho 51-10983; J. P. KOKAI Nos. Sho 51-93224, Sho 55-108667,Sho 55-156953 and Sho 56-36656.

(e) Pyrazoline or pyrazolone derivatives described in U.S. Pat. No.3,180,729; U.S. Pat. No. 4,278,746; J. P. KOKAI Nos. Sho 55-88064, Sho55-88065, Sho 49-105537, Sho 55-51086, Sho 56-80051, Sho 56-8141, Sho57-45545, Sho 54-112637 and Sho 55-74546.

(f) Phenylenediamine derivatives described in U.S. Pat. No. 3,615,404,J. P. KOKOKU Nos. Sho 51-10105, Sho 46-3712 and Sho 47-28336; J.P. KOKAINos. Sho 54-83435, Sho 54-110836 and Sho 54-119925.

(g) Aryl amine derivatives described in U.S. Pat. No. 3,567,450; U.S.Pat. No. 3,180,703; U.S. Pat. No. 3,240,597; U.S. Pat. No. 3,658,520;U.S. Pat. No. 4,232,103; U.S. Pat. No. 4,175,961; U.S. Pat. No.4,012,376; J.P. KOKOKU No. Sho 49-35702; West Germany Patent DAS No.1105181, J.P. KOKOKU No. Sho 39-27577; J. P. KOKAI Nos Sho 55-44250, Sho56-119132 and Sho 56-22437.

(h) Amino substituted chalcone derivatives described in U.S. Pat. No.3,526,501;

(i) N,N-bicarbazyl derivatives described in U.S. Pat. No. 3,542,546;

(j) Oxazol derivatives described in U.S. Pat. No. 3,257,203;

(k) Styryl anthracene derivatives described in J. P. KOKAI NO. Sho56-46234;

(l) Fluorenone derivatives described in J. P. KOKAI No. Sho 54-110837;

(m) Hydrazone derivatives described in U.S. Pat. No. 3,717,462; J. P.KOKAI Nos. Sho 54-59143 (corresponding to U.S. Pat. No. 4,150,987), Sho55-52063, Sho 55-52064, Sho 55-46760, Sho 55-85495, Sho 57-11350, Sho57-148749 and Sho 57-104144.

(n) Benzidine derivatives described in U.S. Pat. No. 4,047,948; U.S.Pat. No. 4,047,949; U.S. Pat. No. 4,265,990; U.S. Pat. No. 4,273,846;U.S. Pat. No. 4,299,897; U.S. Pat. No. 4,306,008.

(o) Stilbene derivatives described in J. P. KOKAI Nos. Sho 58-190953,Sho 59-95540, Sho 59-97148, Sho 59-195658 and Sho 62-36674.

(p) Polyvinylcarbazole and derivatives thereof described in J. P. KOKOKUNo. Sho 34-10966;

(q) Vinyl polymer such as polyvinylpyrene, polyvinylanthracene,poly-2-vinyl-4-(4'-dimethylaminophenyl)-5-phenyl-oxazol,poly-3-vinyl-N-ethylcarbazole in J. P. KOKOKU Nos. Sho 43-18674 and Sho43-19192;

(r) Polymers such as polyacenaphthylene, polyindene, copolymer ofacenaphthylene with styrene in J. P. KOKOKU No. Sho 43-19193;

(s) Condensation polymers such as pyrene-formaldehyde resin,bromopyrene-formaldehyde resin, ethylcarbazol-formaldehyde resindescribed in J. P. KOKAI Nos. Sho 56-13940;

(t) Triphenylmethane polymers described in J. P. KOKAI Nos. Sho 56-90833and Sho 56-161550.

Organic photoconductive compounds should not be limited to the abovecompounds of (a) to (t), and may be any known organic photoconductivecompounds. They may be used alone or in combination containing more thantwo kinds of compounds.

Any known organic and inorganic charge generating agents in the art ofan electrophotographic material may be used as a charge generating agentin the photoconductive layer. Examples of the charge generating agentsinclude selenium, selenium-tellurium, cadmium sulfide, zinc oxide, andthe following organic pigments,

(1) Azo pigments such as monoazo, bisazo and trisazo pigments describedin U.S. Pat. No. 4,436,800, U.S. Pat. No. 4,439,506, J. P. KOKAI Nos.Sho 47-37543, Sho 58-123541, Sho 58-192042, Sho 58-219263, Sho 59-78356,Sho 60-179746, Sho 61-148453 and Sho 61-238063, J. P. KOKOKU No. Sho60-5941 and No. Sho 60-45664;

(2) Phthalocyanine pigments such as nonmetallic or metallicphthalocyanines described in U.S. Pat. No. 3,397,086, U.S. Pat. No.4,666,802, J. P. KOKAI Nos. Sho 51-90827 and Sho 52-55643;

(3) Perylene pigments described in U.S. Pat. No. 3,371,884, J. P. KOKAINos. Sho 47-30330;

(4) Indigo and thioindigo pigments described in British Patent No.2237680, J. P. KOKAI No. Sho 47-30331;

(5) Quinacridone pigments described in British Patents No. 2237680, J.P. KOKAI No. Sho 47-30332;

(6) Polycyclic quinone pigments described in British Patents No.22376789, J. P. KOKAI Nos. Sho 59-184348, Sho 62-28738 and Sho 47-18544;

(7) Bisbenzimidazol pigments described in J. P. KOKAI Nos. Sho 47-30331and Sho 47-18543;

(8) Squarium pigments described in U.S. Pat. No. 4,396,610 and U.S. Pat.No. 4,644,082.

(9) Azulenium pigments described in J. P. KOKAI Nos. Sho 59-53850 andSho 61-21254.

The above mentioned pigments may be used solely or in combination whichcontains two or more of the pigments.

The ratio of the organic photoconductive compound to the binder dependson the compatibility of the photoconductive compound and the binder.Namely, the upper limit of an amount of the organic photoconductivecompound depends on the compatibility of the photoconductive compoundand the binder, and the excess of the organic photoconductive compoundresults in crystallization of the organic photoconductive compound.Since an electrophotographic sensitivity lowers in proportion to theamount of the photoconductive compound, the more organic photoconductivecompound is preferable provided that the organic photoconductivecompound does not crystallize. The organic photoconductive compound maybe contained in an amount of 5-120 parts by weight, preferably 10-100parts by weight per 100 parts by weight of the binder. The organicphotoconductive compound may be used solely, or in combination.

(Sensitizing dyes)

Any sensitizing dyes can be used optionally in the electrophotographicmaterial for color proofing of the present invention depending on kindsof light source for image exposure such as visible light orsemiconductor laser beam. Examples of the sensitizing dyes include:carbonium dye, diphenylmethane dye, triphenylmethane dye, xanthene dye,phthalein dye, polymethine dye (such as oxonol dye, merocyanine cyaninedye, rhodacyanine dye and styryl dye) and phthalocyanine dye which mayinclude metallic atoms and they are described in the followingliteratures: Haruki Miyamoto, Hidehiko Takei, Imaging,1973, (No. 8),page 12, C. J. Young et al., RCA Review, 15, page 469 (1954), KoheiKiyota, Denkitushingakkaironbun, J63-C, (No. 2), page97 (1980), YujiHarazaki et al., Kogyokagakuzasshi, 66, pages 78 and 188 (1963), TadaakiTani, Nihonshashingakkai, 35, page 208 (1972).

Examples of carbonium dyes, triphenylmethane dyes, xanthene dyes andphthalein dyes are described in J. P. KOKOKU No. Sho 51-452, J. P. KOKAINos. Sho 50-90334, Sho 50-114227, Sho 53-39130 and Sho 53-82353, U.S.Pat. Nos. 3,052,540 and 4,054,450, J. P. KOKAI No. Sho 57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes,cyanine dyes and rhodacyanine dyes are described in F. M. Harmmer, TheCyanine Dyes and Related Compounds, US Pat. Nos. 3,047,384, 3,110,591,3,121,008, 3,125,447, 3,128,179, 3,132,942 and 3,622,317, British PatentNos. 1226892, 1309274 and 14045898 and J. P. KOKOKU Nos. Sho 48-7814.andSho 55-18892.

Examples of polymethine dyes which sensitize spectrally in near infraredto infrared region of wavelength of not less than 700 nm are describedin J. P. KOKAI Nos. Sho 47-840 and Sho 47-44180, J. P. KOKOKU Nos. Sho51-41061, Sho 49-5034, Sho 49-45122, Sho 57-46245, Sho 56-35141, Sho57-157254, Sho 61-26044 and Sho 61-27551, U.S. Pat. Nos. 3,619,154 and4,175,956 and "Research Disclosure", 1982, 216, 117-118.

The electrophotographic material of the present invention isadvantageous also in that the performance thereof is not adverselyinfluenced by sensitizing dyes used.

(Other additives)

Further, conventional additives for electrophotographic materials mayoptionally be used in the electrophotographic material of the presentinvention.

Additives include, for example, a chemical sensitizer for improving theelectrophotographic sensitivity, or a plasticizer or a surfactant forimproving film performance.

Examples of chemical sensitizers include: an electron attractivecompound such as halogens, benzoquinone, chloranyl, fluoranyl, bromanyl,dinitrobenzene, anthraquinone, 2,5-dichloro benzoquinone, nitrophenol,tetrachlorophthalic anhydride, 2,3-dichloro-5,6-dicyanobenzoquinone,dinitrofluorenone, trinitrofluorenone, tetracyanoethylene;polyarylalkane compounds, hindered phenol compounds, p-phenylenediaminecompounds described in the following references: Hiroshi Komon, "TheLatest Development and Utilization of Photoconductive Materials andPhotosensitive Materials" chapter 4 to 6; Publishing department ofNihonkagakujouhou Co.,Ltd., (1986); and compounds described in J. P.KOKAI Nos. Sho 58-65439, Sho 58-102239, Sho 58-129439 and Sho 62-71965.

Examples of a plasticizer which can be added in order to improveplasticity of the photoconductive layer include: dimethylphthalate,dibutylphthalate, dioctylphthalate, triphenylphthalate,triphenylphosphate, diisobutyladipate, dimethylsebacate,dibutylsebacate, butyl laurate, methylphtharylethylglycolate anddimethylglycolphthalate. The plasticizer may be added in amount so thatstatic properties of the photoconductive layer are not affectedadversly.

The above mentioned additives are added usually in an amount of0.001-2.0 parts by weight per 100 parts by weight of a photoconductivelayer.

The photoconductive material is ground, and dispersed in a systemcomprising a binder, a solvent thereof and an additive by well knownmethod in the art. For example, it is ground and dispersed in the systemwith the apparatus such as a ball mill, a Kady mill, a sand mill, aDYNO-MILL®, a paint shaker, a roll mill and an ultrasonic dispersionapparatus described in Solomon, "Chemistry of Paint", etc.

Then, they are coated to the substrate, for example, with a barcoater, areversecoater, or Dye coater in suitable coating amount for each imagingmaterial system, and dried.

Solvents used for dispersing the photoconductive material may be anysolvents and determined depending on such factors as the solubility ofthe binder. They may be used solely or in combination.

(Transfer Layer)

The transfer layer will hereunder be illustrated.

The transfer layer comprises a thermoplastic resin with weight-averagemolecular weight of 1×10³ to 1×10⁶, preferably 5×10⁴ to 5×10⁵, and withglass transition temperature of 0° C. to 100° C., preferably 20° to 85°C. Thermoplastic resin is used in an amount of not less than 70% byweight, preferably not less than 90% by weight of the transfer layer.

Examples of the thermoplastic resin include: vinyl chloride resin,polyolefin resin,-olefin-styrene copolymer, vinyl alkanoate resin,polyester resin, polyether resin, acrylic resin, cellulose resin,aliphatic acid modified cellulose resin.

They are described in, for example, the following references:Nikkankogyoshinbunsha, "Plastic Material Lecture", 1 to 18, (1961);Vinyl Department of Kinkikagakukyokai, "Polyvinylchloride", published byNikkankogyoshinbunsha, (1988); Eizo Omori, "Functionality of Acrylicresin", published by Technosystem, (1985); Eiichiro Takiyama, "PolyesterResin Handbook" published by Nikkankogyoshinbunsha (1988); Kazuo Yumoto,"Saturated Polyester Resin Handbook", published byNikkankogyoshinbunsha, (1989); Polymer Society of Japan, "Polymer DataHandbook", Chapter 1, published by Baifukan, (1986); Yuji Harazaki, "Thelatest handbook of binder technology", Chapter 2, published bySogogijutu center (1985).

The thermoplastic resins may be used solely or in combination.

The transfer layer may include other additives in order to improvephysical properties such as coating properties, film-forming propertyand strength of coating. Examples of additives include a plasticizersuch as mentioned above for the photoconductive layer.

The thickness of the transfer layer is 0.1-10 μm, preferably 0.5 to 5μm.

The transfer layer may be applied, for example, by a conventionalcoating method. For example, it is conducted using a coating solutioncontaining an appropriate compound such as one mentioned above and amethod such as one for coating of the photoconductive layer. Inaddition, the transfer layer may be applied by a spray drying methodwhich is known in the art. The above coating methods of the transferlayer are not limitative.

(Preparation of Color Proof)

The method for preparing a color proof using the electrophotographicmaterial for color proofing of the present invention is as follows.First of all, an image to be reproduced is formed on the light-sensitivematerial by a conventional electrophotographic process. Namely,charging, image exposure, development and fixing are conducted by wellknown methods in the art. Any type of developer such as a dry developerand a liquid developer may be used.

Examples of the method are described in, for example, Gen Machida,"Recording Material and Photosensitive Resin", p.107-127, (1983); andGakkaishuppan Center Co.,Ltd., Imaging, No.2-5,"Development.Fixing.Charging.Trasfer in Electrophotography".

A combination of a scanning exposure method wherein an exposure isconducted based on a digital information using a laser beam and adeveloping method using a liquid developer is effective, since it canform a highly precise image.

One of examples will hereunder be described. The electrophotographicmaterial is placed on a flat bed by a register pin method, and is suckedfrom the backside to be fixed. Charging is conducted with a chargingdevice such as one described in the following literature:Electrophotographic Society of Japan, "Fundamentals and Applications ofElectrophotographic Technique", p.212 et seq., published by CoronaCo.,Ltd., in Jun. 15, 1963. Corotron or Scorotron method is generallyused. It is also preferable to control the charging condition byfeedback based on data from means for detecting charging potential, sothat the surface potential may be in an appropriate range.

And then, scanning exposure to laser beams is conducted in accordancewith the manner described in p.254 et seq. of the above mentionedliterature. First of all, the electrophotographic material is exposedusing a dot pattern converted from image for yellow of four colorseparations.

Subsequently, a toner-development is conducted with a liquid developer.Namely, the charged and exposed material is removed from the flat bed,and developed by direct liquid development described in p. 275 et-seq.of the above mentioned literature. The exposure mode is determineddepending on the toner development mode. For example, a negativeexposure is conducted for a reversal development. Namely, an image areais exposed to laser beams, and a development bias voltage is appliedthereto so that a toner may be adsorbed on an image area. The tonershould have the same charging polarity as one of the imaging material oncharging. The detailed information is described in p. 157 et seq. of theabove mentioned literature.

In order to remove the excess developer after development, theelectrophotographic material are squeezed and dried as described in p.283 of the above mentioned literature. It is also preferable to rinsethe material with a liquid carrier for the developer.

Finally, the above procedures are repeated for each color, namelymagenta, cyan, black to form an image with 4 colors on theelectrophotographic material.

The toner image is heat-transfered to the regular paper for printingtogether with the transfer layer to form a color proof.

FIG. 1 shows an apparatus for heat-transfer of a transfer layer to aregular paper. The electrophotographic material is conveyed withappropriate nip pressure between a pair of rubber-coated metallicrollers equipped with a built-in heating means. Temperature on thesurface of the rollers may be 50°-150° C., preferably 80°-120° C. Nippressure between the rollers may be 0.2-20 kgf/cm², preferably 0.5-10kgf/cm². Conveyance speed may be 0.1-100 mm/sec., preferably 1-30mm/sec. The optimum values may be selected depending on the kind of theelectrophotographic materials, namely the physical properties of thetransfer layer, the photoconductive layer and the substrate.

It is preferable to keep the temperature on the surface of the rollersin a range defined above by known means. A means for preheating and/orcooling can be set in front of the heat rollers. Springs or aircylinders which use compressed air as means for pressing (which is notshown in FIG. 1) may also be set on the both ends of an axis of at leastone of rollers.

As described above, the addition of the polymer (P) to thephotoconductive layer can improve releasability of the photoconductivelayer from the transfer layer. As a result, a color proof of highquality without color drift and defect in transfer can be obtained.

Examples of the present invention will hereunder be described in moredetail, but they do not limit the present invention.

In the formulae in the examples, the symbol "-b-" represents that twoblock segments illustrated on both sides of the symbol are present inthe form of blocks to form a block copolymer. Namely, a copolymerrepresented by the formula including the symbol "-b-" is not a randomcopolymer, but a block copolymer.

EXAMPLE P-101

A solution of 70 g of methyl methacrylate, 20 g of methyl acrylate, 10 gof glycidyl methacrylate and 200 g of toluene was heated to 80° C. in astream of nitrogen. 10 g of polymer azobis initiator (I-1) of thefollowing formula was added thereto, and reacted for 8 hours. After thereaction was completed, the reaction mixture was reprecipitated in 1.5 lof methanol. Then, the resultant precipitate was collected, and dried.75 g of Polymer (P-101) was obtained (Mw: 3×10⁴). ##STR37##

EXAMPLE P-012

A solution of 63 g of methyl methacrylate, 12.8 g oftri(dipropyl)silylmethacrylate and 200 g of tetrahydrofuran was degassedsufficiently in a stream of nitrogen, and then cooled to -20° C. 0.8 gof 1,1-diphenyl butyl lithium was added thereto, and reacted for 12hours. Then, a solution of 30 g of the monomer (M-1) of the formula:

    CH.sub.2 ═C(CH.sub.3)(COO(CH.sub.2).sub.2 C.sub.8 F.sub.17)(M-1)

and 60 g of tetrahydrofuran which had been degassed sufficiently instream of nitrogen was added thereto, and reacted for 8 hours. Theresultant reaction mixture was cooled to 0° C. Then, 10 ml of methanolwas added, and reacted for 30 minutes. Then, the polymerization wasceased, and the silyl ester was deblocked. The resultant polymersolution was stirred to 30° C., then 3 ml of 30% ethanol solution ofhydrogen chloride was added, and stirred for 1 hour. Then, the reactionmixture was evaporated to half amount under reduced pressure,reprecipitated in 1 l of petroleum ether. The resultant precipitate wascollected, and dried under reduced pressure. 76 g of Polymer (P-102) wasobtained (Mw: 6.8×10⁴). ##STR38##

EXAMPLE P-103

A solution of 63.8 g of methyl methacrylate, 19.7 g of2-(trifluoroacetyloxy) ethyl methacrylate, 0.5 g of (tetraphenylporphinato)aluminium methyl and 200 g of methylene chloride was heatedto 30° C. in a stream of nitrogen. The resultant reaction mixture wasirradiated with light from 300W-xenon lamp through glass filter from thedistance of 25 cm, and reacted for 20 hours. Then, 25 g of the monomer(M-2) of the following formula was added thereto, and the reactionmixture was irradiated for 12 hours in the same manner as explainedabove. Then, 3 g of methanol was added to the reaction mixture. Thereaction mixture was stirred for 30 minutes, and the reaction wasceased. 50 g of a solution of 5% by weight of p-toluene sulfonic acid intetrahydrofuran was added to the resultant reaction mixture tohydrolize. The resultant mixture was added to 2 l of methanol toprecipitate polymer, and the precipitate was collected and dried. 70 gof Polymer (P-103) was obtained (Mw: 7×10⁴). ##STR39##

EXAMPLE P-104

A mixture of 48 g of ethyl methacrylate, 12 g of glycidyl methacrylateand 2.4 g of benzyl N,N-diethyldithiocarbamate was fed to a vessel,sealed under a stream of nitrogen, heated to 50° C., and then,irradiated with light from 400W-high pressure mercury vapor lamp throughglass filter from the distance of 10 cm for 6 hours to conductphotopolymerization. The resultant mixture was dissolved in 100 g oftetrahydrofuran, and 40 g of the monomer (M-3) of the following formulawas added to the solution of resultant reaction mixture in 100 g oftetrahydrofuran. The vessel was purged with nitrogen, and the radiationwas conducted for 10 hours again. The resultant reaction mixture wasadded to 11 of methanol to precipitate polymer, and the precipitate wascollected and dried. 73 g of Polymer (P-104) was obtained (Mw: 8×10⁴).##STR40##

EXAMPLE P-105

A mixture of 55 g of methyl methacrylate, 20 g of3-(trimethoxysilyl)ethyl methacrylate and 1.0 g of benzyl isopropylxanthate was fed to a vessel in a stream of nitrogen, sealed, heated to50° C., and then, irradiated with light from 400 W-high pressure mercuryvapor lamp through a glass filter from the distance of 10 cm for 6 hoursto conduct photopolymerization. Tetrahydrofuran was added to theresultant to form 40% solution and 25 g of the monomer (M-4) of thefollowing formula was added to the solution. The vessel was purged withnitrogen, and the radiation was conducted for 10 hours. The resultantreaction mixture was added to 2 l of methanol to precipitate polymer,and the precipitate was collected and dried. 63 g of Polymer (P-105) wasobtained (Mw: 6×10⁴. ##STR41##

EXAMPLES P-106˜P-114

Polymers listed in Table 102 were prepared in a similar manner to themethod of Example P-105. Mw of each of resultant polymers (Polymers(P-106)-(P-114)) was in the range of 6×10⁴ to 8×10⁴.

                                      TABLE 102                                   __________________________________________________________________________    Example                                                                            [P]                                                                              AB Type Block Copolymer (ratio by weight)                             __________________________________________________________________________    p-106                                                                              p-106                                                                             ##STR42##                                                                     ##STR43##                                                            p-107                                                                              p-107                                                                             ##STR44##                                                                     ##STR45##                                                            p-108                                                                              p-108                                                                             ##STR46##                                                                     ##STR47##                                                            p-109                                                                              p-109                                                                             ##STR48##                                                                     ##STR49##                                                            p-110                                                                              p-110                                                                             ##STR50##                                                                     ##STR51##                                                            p-111                                                                              p-111                                                                             ##STR52##                                                                     ##STR53##                                                            p-112                                                                              p-112                                                                             ##STR54##                                                                     ##STR55##                                                            p-113                                                                              p-113                                                                             ##STR56##                                                                     ##STR57##                                                            p-114                                                                              p-114                                                                             ##STR58##                                                                     ##STR59##                                                            __________________________________________________________________________

wherein n is an integer of 8 to 10

EXAMPLE P-115

The procedures of Example P-104 were repeated except that 10 g of theinterior (I-2) of the following formula was substituted for benzylN,N-diethyldithiocarbamate. Polymer (P-115) with Mw of 8.3×10⁴ wasobtained. ##STR60##

EXAMPLE P-116:

The procedures of Example P-105 were repeated except that 12 g of theinitiator (I-3) of the following formula was substituted for benzylisopropylxanthate. Polymer (P-116) having Mw of 9.3×10⁴ was obtained.##STR61##

EXAMPLES P-117-P-125

The procedures of Example P-104 were repeated except that 14 g of theinitiator (I-4) of the following formula and monomers corresponding tounits listed in Table 103 were used. Polymers (P-117)-(P-125) having Mwin the range of 7×10⁴ to 9×10⁴ were obtained. ##STR62##

                  TABLE 103                                                       ______________________________________                                         ##STR63##                                                                                                        x/y                                       Exam-                               ratio by                                  ple   [P]     Y                     weight                                    ______________________________________                                        p-117 p-117                                                                                  ##STR64##            40/10                                     p-118 p-118                                                                                  ##STR65##            35/15                                     p-119 p-119                                                                                  ##STR66##            40/10                                     p-120 p-120                                                                                  ##STR67##            45/5                                      p-121 p-121                                                                                  ##STR68##            35.5/12.5                                 p-122 p-122                                                                                  ##STR69##            45/5                                      p-123 p-123                                                                                  ##STR70##            40/10                                     p-124 p-124                                                                                  ##STR71##            40/10                                     p-125 p-125                                                                                  ##STR72##            42.5/7.5                                  ______________________________________                                    

EXAMPLES P-126-P-134

The procedures of Example P-116 were repeated except that 9.6 g of theinitiator (I-5) of the following formula and monomers corresponding tounits listed in Table 104. were used. Polymers (P-126)-(P-134) having Mwin the range of 8×10⁴ ˜10×10⁴ were obtained. ##STR73##

                                      TABLE 104                                   __________________________________________________________________________                                                           x/y/z                  Example                                                                            [P]                                                                              R            R'     Y            Z             ratio by               __________________________________________________________________________                                                           weight                 p-126                                                                              p-126                                                                            CH.sub.2 CF.sub.2 CFHCF.sub.3                                                              CH .sub.3                                                                            --                                                                                          ##STR74##    85/0/15                p-127                                                                              p-127                                                                             ##STR75##   CH.sub.3                                                                              ##STR76##                                                                                  ##STR77##    60/20/20               p-128                                                                              p-128                                                                             ##STR78##   C.sub.2 H.sub.5                                                                      --                                                                                          ##STR79##    85/0/15                p-129                                                                              p-129                                                                            (CH.sub.2)C.sub.8 F.sub.17                                                                 CH.sub.2 C.sub.6 H .sub.5                                                             ##STR80##                                                                                  ##STR81##    75/5/20                p-130                                                                              p-130                                                                            "            C.sub.4 H.sub.9                                                                       ##STR82##                                                                                  ##STR83##    87.5/2.5/10            p-131                                                                              p-131                                                                            "            C.sub.2 H.sub.5                                                                       ##STR84##                                                                                  ##STR85##    90/5/5                 p-132                                                                              p-132                                                                            (CH.sub.2).sub.2 SO.sub.2 NHC.sub.17 F.sub.35                                              C.sub.3 H.sub.7                                                                      --                                                                                          ##STR86##    90/0/10                p-133                                                                              p-133                                                                            (CH.sub.2).sub.2 CO NHC.sub.11 F.sub.23                                                    CH.sub.3                                                                              ##STR87##                                                                                  ##STR88##    65/20/15               p-134                                                                              p-134                                                                             ##STR89##   C.sub.4 H.sub.9                                                                       ##STR90##                                                                                  ##STR91##    80/5/15                __________________________________________________________________________

EXAMPLES P-135-P-138

A mixture of 40 g of monomers corresponding to units listed in Table105, 11 g of the initiator (I-6) of the following formula, and 40 g oftetrahydrofuran was fed to a vessel under a stream of nitrogen, sealed,heated to 50° C., and then, irradiated with light from 400 W-highpressure mercury vapor lamp through a glass filter from the distance of10 cm for 12 hours to conduct photopolymerization. 23 g ofmethylmethacrylate, 22 g of methyl acrylate, and 50% by weight solutionof 15 g of glycidyl methacrylate in tetrahydrofuran were added thereto.The vessel was purged with nitrogen, and the radiation was conducted for10 hours. The resultant reaction mixture was added to 1 l of methanol toprecipitate polymer, and the precipitate was collected and dried.Polymers (P-135)-(P-138) having Mw in the range of 6×10⁴ ˜8×10⁴ wereobtained. ##STR92##

                                      TABLE 5                                     __________________________________________________________________________    Example                                                                             [P] X                  x/y ratio by weight                              __________________________________________________________________________    P-135 P-135                                                                              ##STR93##         60/40                                            P-136 P-136                                                                              ##STR94##         30/70                                            P-137 P-137                                                                              ##STR95##         65/35                                            P-138 P-138                                                                              ##STR96##         70/30                                            __________________________________________________________________________

EXAMPLE P-201

A mixture of 57 g of methyl methacrylate, 28 g of methyl acrylate, 15 gof glycidyl methacrylate, 17.5 g of initiator (I-7) of the followingformula, and 150 g of tetrahydrofuran was heated to 50° C. in a streamof nitrogen. The resultant reaction mixture was irradiated with lightfrom 400 W-high pressure mercury vapor lamp through glass filter fromthe distance of 10 cm for 10 hours to conduct photopolymerization. Theresultant reaction mixture was added to 1.5 1 of methanol to precipitatepolymer, and the precipitate was collected and dried. 72 g of polymerhaving Mw of 4.0×10⁴ was obtained.

40 g of the polymer, 60 g of the monomer (M-5), and 100 g oftetrahydrofuran were heated to 50° C. in a stream of nitrogen. Theresultant reaction mixture was irradiated for 15 hours in the abovementioned manner. The resultant reaction mixture was added to 1.5 l ofmethanol to precipitate polymer, and the precipitate was collected anddried. 78 g of polymer (P-201) having Mw of 6×10⁴ was obtained.##STR97##

EXAMPLES P-202-P-214

The procedures of Example P-201 were repeated except that 0.031 mole ofinitiators listed in Table 202 were substituted for 17.5 g of theinitiator (I-7), 70 to 80 g of polymers (Polymers (P-202)-(P-214))having Mw in the range of 4×10⁴ to 6×10⁴ were obtained,

    TABLE 202      ##STR98##            Example [P] Initiator R      ##STR99##       P-202 P-202      ##STR100##      ##STR101##      ##STR102##      P-203 P-203     ##STR103##      ##STR104##      ##STR105##      P-204 P-204     ##STR106##      ##STR107##      ##STR108##      P-205 P-205     ##STR109##      ##STR110##      ##STR111##      P-206 P-206     ##STR112##      ##STR113##      ##STR114##      P-207 P-207     ##STR115##      ##STR116##      ##STR117##      P-208 P-208     ##STR118##      CH.sub.2 C.sub.6      H.sub.5     ##STR119##       Example [P] Initiator R      ##STR120##       P-209 P-209      ##STR121##      ##STR122##      ##STR123##      P-210 P-210     ##STR124##      ##STR125##      ##STR126##      P-211 P-211     ##STR127##      ##STR128##      ##STR129##      P-212 P-212     ##STR130##      ##STR131##      ##STR132##       Example [P] Initiator [I] R      ##STR133##       P-213 P-213      ##STR134##      ##STR135##      ##STR136##      P-214 P-214     ##STR137##      ##STR138##      ##STR139##

EXAMPLES (P-215)-(P-233)

The procedures of Example P-201 were repeated except that 60 g ofmonomers corresponding to units listed in Table 203 for 60 g of themonomer (M-5). Mw of each of resultant polymers (Polymers(P-215)-(P-233)) was in the range of 6×10⁴ ˜7×10⁴.

                  TABLE 203                                                       ______________________________________                                         ##STR140##                                                                    ##STR141##                                                                   Example                                                                              [P]     Y                                                              ______________________________________                                        P-215  P-215                                                                                  ##STR142##                                                    P-216  P-216                                                                                  ##STR143##                                                    P-217  P-217                                                                                  ##STR144##                                                    P-218  P-218                                                                                  ##STR145##                                                    P-219  P-219                                                                                  ##STR146##                                                    P-220  P-220                                                                                  ##STR147##                                                    P-221  P-221                                                                                  ##STR148##                                                    P-222  P-222                                                                                  ##STR149##                                                    P-223  P-223                                                                                  ##STR150##                                                    P-224  P-224                                                                                  ##STR151##                                                    P-225  P-225                                                                                  ##STR152##                                                    P-226  P-226                                                                                  ##STR153##                                                    P-227  P-227                                                                                  ##STR154##                                                    P-228  P-228                                                                                  ##STR155##                                                    P-229  P-229                                                                                  ##STR156##                                                    P-230  P-230                                                                                  ##STR157##                                                    P-231  P-231                                                                                  ##STR158##                                                    P-232  P-232                                                                                  ##STR159##                                                    P-233  P-233                                                                                  ##STR160##                                                    ______________________________________                                    

EXAMPLES P-234-P-240

The procedures of Example P-201 were repeated except for using a mixtureof 70 g of methacrylate monomer, 30 g of monomers corresponding to unitslisted Table 204, 15 g of the initiator (I-13), and 100 g oftetrahydrofuran. 80 g of polymers having Mw of 6×10⁴ ˜7×10⁴ wereobtained.

Further, polymerization was conducted using a mixture of 50 g of theresultant polymer, 50 g of the monomer (M-5), and 100 g oftetrahydrofuran in the same manner as a method of Example P-201 exceptfor substituting diethylether for methanol. Mw of each of resultantpolymers (Polymers (P-234)-(P-240)) was in the range of 8×10⁴ to 10×10⁴.

                                      TABLE 204                                   __________________________________________________________________________     ##STR161##                                                                    ##STR162##                                                                   Example                                                                             [P]  R       Y                                                          __________________________________________________________________________    P-234 P-234                                                                              C.sub.2 H.sub.5                                                                        ##STR163##                                                P-235 P-235                                                                              CH.sub.3                                                                               ##STR164##                                                P-236 P-236                                                                              CH.sub.2 C.sub.6 H.sub.5                                                               ##STR165##                                                P-237 P-237                                                                               ##STR166##                                                                            ##STR167##                                                P-238 P-238                                                                              C.sub.4 H.sub.9                                                                        ##STR168##                                                P-239 P-239                                                                              CH.sub.3                                                                               ##STR169##                                                P-240 P-240                                                                              C.sub.2 H.sub.5                                                                        ##STR170##                                                __________________________________________________________________________

EXAMPLES P-241-P-254

The procedures of Example P-201 were repeated to prepare polymers havingthe structure of the following formula except for using 10 g Of theinitiator (I-9) for 17.5 g of the initiator (I-7), and diethylether formethanol as a solvent for reprecipitation. Polymers (P-241)-(P-254)having Mw in the range of 7×10⁴ ˜9×10⁴ were obtained. ##STR171## wherein[P] represents a polymer chain having the following structures.

                                      TABLE 205                                   __________________________________________________________________________     ##STR172##                                                                   __________________________________________________________________________    Polymer (P-241)                                                                ##STR173##                                                                   Polymer (P-242)                                                                ##STR174##                                                                   Polymer (P-243)                                                                ##STR175##                                                                   Polymer (P-244)                                                                ##STR176##                                                                   Polymer (P-245)                                                                ##STR177##                                                                   Polymer (P-246)                                                                ##STR178##                                                                   Polymer (P-247)                                                                ##STR179##                                                                   Polymer (P-248)                                                                ##STR180##                                                                   Polymer (P-249)                                                                ##STR181##                                                                   Polymer (P-250)                                                                ##STR182##                                                                   Polymer (P-251)                                                                ##STR183##                                                                   Polymer (P-252)                                                                ##STR184##                                                                   Polymer (P-253)                                                                ##STR185##                                                                   Polymer (P-254)                                                                ##STR186##                                                                   __________________________________________________________________________

EXAMPLE P-301

A mixture of 60 g of methyl methacrylate, 30 g of a macromonomer (M-6)of the following formula, 10 g of diglycidyl methacrylate, and 150 g oftoluene was heated to 70° C. in a stream of nitrogen. 1.0 g of2,2'-azobis(isobutylonytrile) (A.I.B.N) was added and reacted for 4hours. Further, 0.5 g of A.I.B.N was added and reacted for 4 hours.Polymer having Mw of 6.5×10⁴ (P-301) was obtained. ##STR187##

EXAMPLES P-302-P-314

The procedures of Example P-301 were repeated except that 30 g ofmacromonomers listed in Table 302 for 30 g of the macromonomer (M-6).Polymers (P-302)-(P-314) having Mw in the range of 5×10⁴ ×8×10⁴ wereobtained. Mw of used macromonomers are listed in Table 302.

                                      TABLE 302                                   __________________________________________________________________________     ##STR188##                                                                   Example                                                                            [P] Y                         Mw of Macromonomer                         __________________________________________________________________________    P-302                                                                              P-302                                                                              ##STR189##               6.5 × 10.sup.3                       P-303                                                                              P-303                                                                              ##STR190##               8 × 10.sup.3                         P-304                                                                              P-304                                                                              ##STR191##               6 × 10.sup.3                         P-305                                                                              P-305                                                                              ##STR192##               8 × 10.sup.3                         P-306                                                                              P-306                                                                              ##STR193##               5 × 10.sup.3                         P-307                                                                              P-307                                                                              ##STR194##               8 × 10.sup.3                         P-308                                                                              P-308                                                                              ##STR195##               7 × 10.sup.3                         P-309                                                                              P-309                                                                              ##STR196##               6 × 10.sup.3                         P-310                                                                              P-310                                                                              ##STR197##               9 × 10.sup.3                         P-311                                                                              P-311                                                                              ##STR198##               1.5 × 10.sup.4                       P-312                                                                              P-312                                                                              ##STR199##               1.2 × 10.sup.4                       P-313                                                                              P-313                                                                              ##STR200##               1.5 × 10.sup.4                       P-314                                                                              P-314                                                                              ##STR201##               1.0 × 10.sup.4                       __________________________________________________________________________

EXAMPLES P-315-P-325

A mixture of monomers corresponding to units listed in Table 303, 25 gof Macromonomer FM-0721 (Mw 1×10⁴, manufactured by CHISSO CORPORATION),and 200 g of toluene was heated to 80° C. in a stream of nitrogen.

                                      TABLE 303                                   __________________________________________________________________________     ##STR202##                                                                                                                          x/y/z                  Example                                                                            [P]   R      X             Y                      ratio by               __________________________________________________________________________                                                           weight                 P-315                                                                              P-315 CH.sub.2 C.sub.6 H.sub.5                                                             --                                                                                           ##STR203##            55/0/20                P-316                                                                              P-316 CH.sub.3                                                                             --                                                                                           ##STR204##            60/0/15                P-317                                                                              P-317 CH.sub.3                                                                              ##STR205##                                                                                  ##STR206##            50/15/10               P-318                                                                              P-318 CH.sub.2 C.sub.6 H.sub.5                                                              ##STR207##                                                                                  ##STR208##            55/10/10               P-319                                                                              P-319 CH.sub.3                                                                              ##STR209##                                                                                  ##STR210##            65/5/5                 P-320                                                                              P-320 C.sub.2 H.sub.5                                                                      --                                                                                           ##STR211##            65/0/10                P-321                                                                              P-321 C.sub.4 H.sub.9                                                                       ##STR212##                                                                                  ##STR213##            50/10/15               P-322                                                                              P-322 C.sub.2 H.sub.5                                                                      --                                                                                           ##STR214##            67/0/8                 P-323                                                                              P-323 C.sub.6 H.sub.5                                                                      --                                                                                           ##STR215##            65/0/10                P-324                                                                              P-324 CH.sub.3                                                                              ##STR216##                                                                                  ##STR217##            54/14/15               P-325                                                                              P-325 C.sub.2 H.sub.5                                                                      --                                                                                           ##STR218##            55/0/20                __________________________________________________________________________

EXAMPLES P-326-P-337

The procedures of Example P-301 were repeated except for using a mixtureof a monomer of the following formula (M-7), macromonomers listed inTable 304 and 200 g of toluene. Polymers (P-326)-(P-337) having in therange of Mw of 6×10⁴ ˜8×10⁴ were obtained. ##STR219##

                                      TABLE 304                                   __________________________________________________________________________             x/y                                              Mw of                        ratio by                                         Macro-              Example                                                                            [P] weight                                                                             M                                           monomer             __________________________________________________________________________    P-326                                                                              P-326                                                                             60/40                                                                               ##STR220##                                   9 ×                                                                   10.sup.3            P-327                                                                              P-327                                                                             80/20                                                                               ##STR221##                                 1.4 ×                                                                   10.sup.4            P-328                                                                              P-328                                                                             80/20                                                                               ##STR222##                                   8 ×                                                                   10.sup.3            P-329                                                                              P-329                                                                             75/25                                                                               ##STR223##                                   9 ×                                                                   10.sup.4            P-330                                                                              P-330                                                                             80/20                                                                               ##STR224##                                 1.1 ×                                                                   10.sup.4            P-331                                                                              P-331                                                                             90/10                                                                               ##STR225##                                   3 ×                                                                   10.sup.3            P-332                                                                              P-332                                                                             60/40                                                                               ##STR226##                                   1 ×                                                                   10.sup.4            P-333                                                                              P-333                                                                             50/50                                                                               ##STR227##                                   7 ×                                                                   10.sup.3            P-334                                                                              P-334                                                                             80/20                                                                               ##STR228##                                   8 ×                                                                   10.sup.3            P-335                                                                              P-335                                                                             75/25                                                                               ##STR229##                                   8 ×                                                                   10.sup.3            P-336                                                                              P-336                                                                             80/20                                                                               ##STR230##                                   6 ×                                                                   10.sup.3            P-337                                                                              P-337                                                                             75/25                                                                               ##STR231##                                   8 ×                                                                   10.sup.3            __________________________________________________________________________

EXAMPLE P-401

A mixture of 50 g of a monomer (M-8) of the following formula, 0.5 g ofan initiator (I-21) of the following formula and 50 g of tetrahydrofuranwas fed to a vessel and sealed in a stream of nitrogen, and heated to60° C., and then, irradiated with light from 400 W-high pressure mercuryvapor lamp through a glass filter from the distance of 10 cm for 10hours to conduct photopolymerization. A mixture of 25 g ofmethylmethacrylate, 15 g of glycidyl methacrylate and 10 g ofmacromonomer (M-9) of the following formula, and 50 g of tetrahydrofuranwas added thereto. Then, the vessel was purged with nitrogen, and theradiation was conducted for 16 hours. The resultant reaction mixture wasadded to 1.0 1 of methanol to precipitate polymer, and the precipitatewas collected and dried. 68 g of Polymer (P-401) having Mw of 6×10⁴ wasobtained. ##STR232##

EXAMPLE P-402

A mixture of 36 g of the monomer (M-10) of the following formula, 4 g ofa siloxane macromonomer praqcell FM-725 (manufactured by CHISSOCORPORATION, Mw 1×10⁴), 1.0 g of an initiator (I-22) of the followingformula and 50 g of tetrahydrofuran are charged to a vessel and sealedin a flow of nitrogen, and heated 50° C. Then, the mixture wasirradiated for 12 hours in the same manner as Example 401 to conductphotopolymerization. A mixture of 24 g of methyl methacrylate, 18 g ofmethyl acrylate, and 18 g of glycidyl methacrylate and 60 g oftetrahydrofuran was added to the mixture. And then, the vessel waspurged with nitrogen, and was irradiated for 12 hours in the same manneras Example P-401.

The resultant reaction mixture was added to 1 l of methanol toprecipitate polymer. The precipitate was collected and dried. 70 g ofpolymer (Polymer (P-402)) with Mw of 8×10⁴ was obtained. ##STR233##

EXAMPLE P-403

A mixture of 25 g of methyl methacrylate, 15 g of glycidyl methacrylate,10 g of a macromonomer (M-11) of the following formula, 2.5 g of aninitiator (I-23) of the following formula, and 50 g of tetrahydrofuranwas degassed in a stream of nitrogen, and irradiated for 12 hours in thesame manner as Example P-401.

A solution of 50 g of a monomer (M-12) of the following formula and 60 gof tetrahydrofuran was added to the resultant reaction mixture and thenthe vessel was purged with nitrogen, and the radiation was conducted for12 hours. The resultant reaction mixture was added to 1 l of methanol toprecipitate. The precipitate was collected and dried. 72 g of polymer(Polymer (P-403)) having Mw of 5.3×10⁴ was obtained. ##STR234##

EXAMPLE P-404-P-416

The procedures of Example P-402 were repeated except for substitutingmacromonomers corresponding to the macromonomer segment (MA) listed inTable 402 for a macromonomer. Polymers (P-404)-(P-416) having Mw in therange of 5×10⁴ ˜8×10⁴ were obtained. Mw of macromonomers which were usedare also listed in Table 402.

                                      TABLE 402                                   __________________________________________________________________________     ##STR235##                                                                   Example                                                                              Polymer                                                                              Macromonomer segment (M.sub.A)                                                                 Mw of Macromonomer                             __________________________________________________________________________    404    P-404   M.sub.A -4 *)   6.5 × 10.sup.3                           405    P-405   M.sub.A -5 *)   8 × 10.sup.3                             406    P-406   M.sub.A -6 *)   6 × 10.sup.3                             407    P-407   M.sub.A -7 *)   8 × 10.sup.3                             408    P-408   M.sub.A -8 *)   5 × 10.sup.3                             409    P-409   M.sub.A -9 *)   8 × 10.sup.3                             410    P-410  M.sub.A -10 *)   7 × 10.sup.3                             411    P-411  M.sub.A -11 *)   6 × 10.sup.3                             412    P-412  M.sub.A -12 *)   9 × 10.sup.3                             413    P-413  M.sub.A -13 *)   1.5 × 10.sup.3                           414    P-414  M.sub.A -14 *)   1.2 × 10.sup.3                           415    P-415  M.sub.A -15 *)   1.5 × 10.sup.3                           416    P-416  M.sub.A -16 *)   1.0 × 10.sup.3                           __________________________________________________________________________    *) Units of X (the macromonomer segment (M.sub.A)) are as follows:            (M.sub.A -4)                                                                   ##STR236##                                                                   (M.sub.A -5)                                                                   ##STR237##                                                                   (M.sub.A -6)                                                                   ##STR238##                                                                   (M.sub.A -7)                                                                   ##STR239##                                                                   (M.sub.A -8)                                                                   ##STR240##                                                                   (M.sub.A -9)                                                                   ##STR241##                                                                   (M.sub.A -10)                                                                  ##STR242##                                                                   (M.sub.A -11)                                                                  ##STR243##                                                                   (M.sub.A -12)                                                                  ##STR244##                                                                   (M.sub.A -13)                                                                  ##STR245##                                                                   (M.sub.A -14)                                                                  ##STR246##                                                                   (M.sub.A -15)                                                                  ##STR247##                                                                   (M.sub.A -16)                                                                  ##STR248##                                                               

Polymers listed in Table 403 were prepared by a similar method to one ofExample P-401. Polymers (P-417)-(P-427) having Mw of 4×10⁴ ˜8×10⁴ wereobtained. Mw of each of one-functional macromonomers corresponding tounits (M_(B) -17) to (M_(B) -29) which were used for the preparation wasin the range of 6×10³ ˜1×10⁴.

                                      TABLE 403                                   __________________________________________________________________________     ##STR249##                                                                            Y                                                                             ratio by                                                             Example                                                                            [P] weight                                                                             Z                                                               __________________________________________________________________________    P-417                                                                              P-417                                                                             M.sub.B -17                                                                         ##STR250##                                                     P-418                                                                              P-418                                                                             M.sub.B -18                                                                         ##STR251##                                                     P-419                                                                              P-419                                                                             M.sub.B -19                                                                         ##STR252##                                                     P-420                                                                              P-420                                                                             M.sub.B -20                                                                         ##STR253##                                                     P-421                                                                              P-421                                                                             M.sub.B -21                                                                         ##STR254##                                                     P-422                                                                              P-422                                                                             M.sub.B -22                                                                         ##STR255##                                                     P-423                                                                              P-423                                                                             M.sub.B -23                                                                         ##STR256##                                                     P-424                                                                              P-424                                                                             M.sub.B -24                                                                         ##STR257##                                                     P-425                                                                              P-425                                                                             M.sub.B -25                                                                         ##STR258##                                                     P-426                                                                              P-426                                                                             M.sub.B -26                                                                         ##STR259##                                                     P-427                                                                              P-427                                                                             M.sub.B -27                                                                         ##STR260##                                                     P-428                                                                              P-428                                                                             M.sub.B -28                                                                         ##STR261##                                                     P-429                                                                              P-429                                                                             M.sub.B -29                                                                         ##STR262##                                                     __________________________________________________________________________    *) (M.sub.B -17) to (M.sub.B -29) are as follows:                             (M.sub.B -17)                                                                  ##STR263##                                                                   (M.sub.B -18)                                                                  ##STR264##                                                                   (M.sub.B -19)                                                                  ##STR265##                                                                   (M.sub.B -20)                                                                  ##STR266##                                                                   (M.sub.B -21)                                                                 (M.sub.B -22)                                                                  ##STR267##                                                                   (M.sub.B -23)                                                                  ##STR268##                                                                   (M.sub.B -24)                                                                  ##STR269##                                                                   (M.sub.B -25)                                                                  ##STR270##                                                                   (M.sub.B -26)                                                                  ##STR271##                                                                   (M.sub.B -27)                                                                  ##STR272##                                                                   (M.sub.B -28)                                                                  ##STR273##                                                                   (M.sub.B -29)                                                                  ##STR274##                                                               

The following Examples Q-1 to 35 are for the polymer (Q₁).

EXAMPLE Q-1

A solution of 80 g of benzyl methacrylate, 20 g of macromonomer havingthe following structure (Weight-average molecular weight (Mw): 6×10³)and 100 g of toluene was heated to 80° C. in a stream of nitrogen. 6.0 gof 2,2'-azobis(valeronytrile) (A.I.V.N.) was added thereto, and reactedfor 3 hours. Then, 1 g of A.I.V.N. was further added thereto, andreacted for 4 hours. Mw of the resultant polymer (Polymer (Q-1)) was9.5×10³. ##STR275##

EXAMPLE Q-2

A solution of 60 g of methyl methacrylate, 25 g of macromonomer havingthe following structure (Mw: 5×10³), 15 g of methyl acrylate, 130 g oftoluene and 20 g of ethanol was heated to 80° C. in a stream ofnitrogen. 7 g of azobis(valeric acid) (A.C.V.) was added thereto, andreacted for 4 hours. Then, 1 g of A.C.V. was further added thereto, andreacted for 4 hours. Mw of the resultant polymer (Polymer (Q-2)) was1×10⁴. ##STR276##

EXAMPLE Q-3

A solution of 70 g of 2-chlorophenyl methacrylate, 25 g of macromonomerhaving the following structure (Mw:6.5×10³), 2 g of thioglycolic acidand 150 g of toluene was heated to 75° C. in a stream of nitrogen. 1 gof 2,2'-azobis(isobutyronitrile) (A.I.B.N.) was added thereto, andreacted for 4 hours. Then, 0.8 g of A.I.B.N. was added thereto, andreacted for 3 hours. Then, 0.5 g of A.I.B.N. was further added thereto,and reacted for 4 hours. Mw of the resultant polymer (Polymer (Q-3)) was7.8×10⁴. ##STR277##

EXAMPLES Q-4-Q-11

Polymers (Q-4)-(Q-11) listed in Table 2 were prepared using themethacrylates and the macromonomers corresponding to the structure shownin Table 2 in a similar manner to the method of Example Q-1.

Mw of each of resultant polymers (Polymers (Q-4)-(Q-11)) was in therange of 7×10³ to 1×10⁴.

Mw of each of the macromonomers used was in the range of 5×10⁵ to 7×10³.

                                      TABLE 2                                     __________________________________________________________________________     ##STR278##                                                                                                  x/y ratio by                                   Example                                                                            [Q] R         R'          weight Y                                       __________________________________________________________________________    Q-4  Q-4 C.sub.2 H.sub.5                                                                          ##STR279## 95/5                                                                                  ##STR280##                             Q-5  Q-5 C.sub.3 H.sub.7                                                                          ##STR281##  90/10                                                                                ##STR282##                             Q-6  Q-6 C.sub.4 H.sub.9                                                                          ##STR283## 95/5                                                                                  ##STR284##                             Q-7  Q-7                                                                                ##STR285##                                                                             CH.sub.3    94/6                                                                                  ##STR286##                             Q-8  Q-8                                                                                ##STR287##                                                                             C.sub.2 H.sub.5                                                                           94/6                                                                                  ##STR288##                             Q-9  Q-9                                                                                ##STR289##                                                                             CH.sub.3    96/4                                                                                  ##STR290##                             Q-10  Q-10                                                                             CH.sub.3                                                                                 ##STR291## 96/4                                                                                  ##STR292##                             Q-11  Q-11                                                                             CH.sub.3  C.sub.2 H.sub.5                                                                           92/8                                                                                  ##STR293##                             __________________________________________________________________________

EXAMPLES Q-12-Q-19

Polymers (Q-12)-(Q-19) listed in Table 3 were prepared in a similarmanner to the method of Example Q-2.

Mw of each of resultant polymers (Polymers (Q-12)-(Q-19)) was in therange of 8×10³ to 1×10⁴.

Mw of each of the macromonomers used was in the range of 4×10³ to 6×10³.

    TABLE 3      ##STR294##      Example [Q] W.sub.2 R x/y Z R' Y x'/y'               Q-12 Q-12      ##STR295##      C.sub.2      H.sub.5 70/30     ##STR296##      ##STR297##      ##STR298##      92/8  Q-13 Q-13 " C.sub.3 H.sub.7 75/25 " CH.sub.2 C.sub.6 H.sub.5      ##STR299##       90/10  Q-14 Q-14 " C.sub.2 H.sub.5 90/10 (CH.sub.2).sub.2      OOC(CH.sub.2).sub.2      S     ##STR300##      ##STR301##      94/6  Q-15 Q-15 " CH.sub.2 C.sub.6 H.sub.5 85/15 (CH.sub.2).sub.2 S     C.sub.2      H.sub.5     ##STR302##      92/8      Q-16 Q-16     ##STR303##      ##STR304##      88/12 (CH.sub.2).sub.2 S C.sub.4      H.sub.9     ##STR305##       90/10      Q-17 Q-17     ##STR306##      C.sub.2      H.sub.5 85/15 "     ##STR307##      ##STR308##      95/5      Q-18 Q-18     ##STR309##      C.sub.3      H.sub.7 80/20     ##STR310##      ##STR311##      ##STR312##       90/10      Q-19 Q-19     ##STR313##      CH.sub.2 C.sub.6      H.sub.5 85/15     ##STR314##      ##STR315##      ##STR316##      93/7     X/Y: ratio by weight

EXAMPLES Q-20-Q-27

Polymers (Q-20)-(Q-27) listed in Table 4 were prepared in a similarmanner to the method of Example Q-3.

Mw of each of resultant polymers (Polymers (Q-20)-(Q-27)) was in therange of 7×10³ to 1×10⁴.

Mw of each of the macromonomers used was in the range of 3×10³ to 6×10⁴.

    TABLE 4      ##STR317##           x/y ratio by  Example [Q] W.sub.1 R R' weight Y             Q-20 Q-20 HOOCH.sub.2      CS     ##STR318##      C.sub.2      H.sub.5 96/4     ##STR319##      Q-21 Q-21     ##STR320##      ##STR321##      ##STR322##      95/5      ##STR323##      Q-22 Q-22     ##STR324##      CH.sub.3      ##STR325##      90/10     ##STR326##      Q-23 Q-23     ##STR327##      C.sub.2      H.sub.5     ##STR328##      92/8      ##STR329##       Q-24 Q-24 (C.sub.2 H.sub.5).sub.3 N.HO.sub.3 SCH.sub.2 CH.sub.2 S      ##STR330##      C.sub.4 H.sub.9      90/10     ##STR331##      Q-25 Q-25     ##STR332##      ##STR333##      C.sub.2      H.sub.5 93/7     ##STR334##       Q-26 Q-26 HOOC(CH.sub.2).sub.2      S     ##STR335##      C.sub.3      H.sub.7 93/5     ##STR336##      Q-27 Q-27     ##STR337##      ##STR338##      ##STR339##      85/15     ##STR340##

EXAMPLES Q-28-Q-35

Polymers (Q-28)-(Q-35) listed in Table 5 were prepared by polymerizingsolutions of 20 g of the macromonomers and 80 g of the monomerscorresponding to the units shown in Table 5, 2 g of thiosalicylic acid,130 g of toluene and 20 g of ethanol in a similar manner to the methodof Example Q-3.

Mw of each of resultant polymers (Polymers (Q-28)-(Q-35)) was in therange of 6×10³ to 8.5×10³.

                                      TABLE 5                                     __________________________________________________________________________     ##STR341##                                                                   Example                                                                              (Q)                                                                             R         Y              Z                x/y/z                      __________________________________________________________________________    Q-28  Q-28                                                                             CH.sub.3                                                                                 ##STR342##    --               60/20/10                   Q-29  Q-29                                                                             CH.sub.3                                                                                 ##STR343##                                                                                   ##STR344##      57.5/20/2.5                Q-30  Q-30                                                                             CH.sub.3                                                                                 ##STR345##                                                                                   ##STR346##      55/15/10                   Q-31  Q-31                                                                             CH.sub.2 C.sub.6 H.sub.5                                                                 ##STR347##                                                                                   ##STR348##      63/15/2                    Q-32  Q-32                                                                             C.sub.2 H.sub.5                                                                          ##STR349##    --               70/10/0                    Q-33  Q-33                                                                             C.sub.4 H.sub.9                                                                          ##STR350##    --               75/5/0                     Q-34  Q-34                                                                             (CH.sub.2).sub.2 C.sub.6 H.sub.5                                                         ##STR351##                                                                                   ##STR352##      30/40/10                   Q-35  Q-35                                                                             C.sub.6 H.sub.5                                                                          ##STR353##                                                                                   ##STR354##      67/10/3                    __________________________________________________________________________

The following Examples M-1 to M-5 are for the macromonomer (M_(D)) andExamples Q-36 to Q-70 are for the polymer (Q2).

Example M-13

A solution of 30 g of triphenylmethyl methacrylate and 100 g of toluenewas sufficiently degased in a stream of nitrogen and cooled to -20° C.Then 1.0 g of 1,1 -diphenylbutyllithium was added thereto to react for10 hours.

Then a solution of 70 g of ethyl methacrylate and 100 g of toluenesufficiently degased in a stream of nitrogen was added to this solution.After reacting for 10 hours, the polymerization reaction was ceased bycooling the solution to 0° C. and then passing carbon dioxide gasthrough the solution for 30 minutes at flow rate of 60 ml/mim.

The resultant polymer solution was stirred to 25° C. , 6 g of2-hydroxyethyl methacrylate was added thereto, then a solution of 12 gof dicyclohexylcarbodiimide, 1.0 g of 4-N,N-dimethylaminopyridine and 20g of methylene dichloride was added thereto dropwise over 30 minutes.

After removing insoluble matter by filtration, 10 ml of 30% ethanolsolution of hydrogen chloride was added, and stirred for 1 hour. Thenthe reaction mixture was evaporated to half amount under reducedpressure, reprecipitated in 1 l of petroleum ether. The resultantprecipitate was collected, and dried under reduced pressure. 56 g ofmacromonomer (M-13) was obtained (Mw: 6.5×10³). ##STR355##

Example M-14

A solution of 5 g of benzyl methacrylate, 0.1 g of (tetraphenylporphinato)aluminium methyl and 60 g of methylene chloride was heated to30° C. in a stream of nitrogen. The resultant reaction mixture wasirradiated with light from 300 W-xenon lamp through glass filter fromthe distance of 25 cm, and reacted for 12 hours. Then, 45 g of butylmethacrylate was added thereto, and the reaction mixture was irradiatedfor 8 hours in the same manner as explained above. Then, 10 g of4-bromomethylstyrene was added to the reaction mixture. The reactionmixture was stirred for 30 minutes, and the reaction was ceased. Then,Pd--C was added to the reaction mixture and catalytic reduction wascarried out at 25° C. for 1 hour.

After removing insoluble matter by filtration, the resulting mixture wasreprecipitated in 500 ml of petroleum ether. The resultant precipitatewas collected, and dried under reduced pressure. 33 g of macromonomer(M-14) was obtained (Mw: 7×10³). ##STR356##

EXAMPLE M-15

A solution of 20 g of 4-vinylphenyloxytrimethylsilane and 100 g oftoluene was sufficiently degased in a stream of nitrogen and cooled at0° C. 2 g of 1,1-diphenyl-3-methylpentyllithium was added to thissolution. After stirring for 6 hours, a solution of 80 g of2-chloro-6-methylpentyl methacrylate and 100 g of toluene sufficientlydegased in a stream of nitrogen was added thereto. After reacting for 8hours, ethylene oxide was passed through the reaction mixture at flowrate of 30 ml/min for 30 minutes with sufficiently stirring. Then, 12 gof methacryloyl chloride maintained at 15° C. was added to the reactionmixture dropwise over 30 minutes.

After stirring for 3 hours, 10 g of 30% ethanol solution of hydrogenchloride was added, and stirred for 1 hour at 25° C. Then the reactionmixture was reprecipitated in 1 l of petroleum ether. The resultantprecipitate was collected and washed with 300 ml of diethyl ether twotimes, and dried under reduced pressure. 55 g of macromonomer (M-15) wasobtained (Mw: 7.8×10³). ##STR357##

EXAMPLE M-16

A solution of 40 g of triphenylmethyl methacrylate and 100 g of toluenewas sufficiently degased in a stream of nitrogen and cooled at -20° C.

2 g of sec-butyllithium was added to the solution. After reacting for 10hours, a solution of 60 g of styrene and 100 g of toluene sufficientlydegased in a stream of nitrogen was added thereto. After reacting for 12hours, 11 g of benzyl bromide was added thereto after cooling thereaction mixture to 0° C., and the reaction mixture was stirred for 1hour at the same temperature and then for 2 hours at 25° C. Then, 10 gof 30% ethanol solution of hydrogen chloride was added, and stirred for2 hours.

After removing insoluble matter by filtration, the resulting mixture wasreprecipitated in 1 l of n-hexane. The resultant precipitate wascollected, and dried under reduced pressure. 58 g of macromonomer (M-16)was obtained (Mw: 4.5×10⁵). ##STR358##

EXAMPLE M-17

A mixture of 70 g of phenyl methacrylate and 4.8 g of benzylN-hydroxylethyl-N-ethyldithiocarbamate was fed to a vessel, sealed undera stream of nitrogen, heated to 60° C., and then, irradiated with lightfrom 400 W-high pressure mercury vapor lamp through glass filter fromthe distance of 10 cm for 10 hours to conduct photopolymerization. Afteraddition of 30 g of acrylic acid and 180 g of methylethylketone thereto,the vessel was purged with nitrogen, and the radiation was conducted for10 hours again. To the resultant reaction mixture 12 g of 2-cyanatoethylmethacrylate was added dropwise over 1 hour at 0° C. and stirred for 2hours.

The resulting mixture was reprecipitated in 1.5 l of n-hexane. Theresultant precipitate was collected, and dried. 68 g of macromonomer(M-17) was obtained (Mw: 6.0×10³). ##STR359##

The following Examples Q-36 to 70 are for the polymer (Q₂).

EXAMPLE Q-36

A solution of 80 g of ethyl methacrylate, 120 g of macromonomer (M-13)and 150 g of toluene was heated to 95° C. in a stream of nitrogen. Then,6 g of 2,2'-azobis(isobutyronitrile) (A.I.B.N.) was added thereto, andreacted for 3 hours. Then, 2 g of A.I.B.N. was further added theretoevery 2 hours, and reacted.

Mw of the resultant polymer (Polymer (Q-36)) was 9×10³. ##STR360##

EXAMPLE Q-37

A solution of 70 g of 2-chlorophenyl methacrylate, 30 g of macromonomer(M-14), 2 g of n-dodecylmercaptan and 100 g of toluene was heated to 80°C. in a stream of nitrogen. Then, 3 g of 2,2'-azobis(valeronytrile)(A.I.V.N.) was added thereto, and reacted for 3 hours. Then, 1 g ofA.I.V.N. was added thereto, and reacted for 2 hours. Then, 1 g ofA.I.V.N. was further added thereto and the solution was heated to 90° C., and reacted for 3 hours. Mw of the resultant polymer (Polymer (Q-37))was 7.6×10³. ##STR361##

EXAMPLES Q-38-Q-53

The procedures of Example Q-36 were repeated except that methacrylateslisted in Table 6 were substituted for ethyl methacrylate. Mw of each ofresultant polymers (Polymers (Q-38)-(Q-53)) was in the range of 5×10³ to9×10³.

                                      TABLE 6                                     __________________________________________________________________________     ##STR362##                                                                   Example                                                                            (Q) R               Y             z/y                                    __________________________________________________________________________    Q-38 Q-38                                                                              C.sub.4 H.sub.9 --            80/0                                   Q-39 Q-39                                                                              CH.sub.2 C.sub.6 H.sub.5                                                                      --            80/0                                   Q-40 Q-40                                                                              C.sub.6 H.sub.5 --            80/0                                   Q-41 Q-41                                                                              C.sub.4 H.sub.9                                                                                ##STR363##    65/15                                 Q-42 Q-42                                                                              CH.sub.2 C.sub.6 H.sub.5                                                                       ##STR364##    70/10                                 Q-43 Q-43                                                                               ##STR365##     --            80/0                                   Q-44 Q-44                                                                               ##STR366##     --            80/0                                   Q-45 Q-45                                                                               ##STR367##     --            80/0                                   Q-46 Q-46                                                                               ##STR368##     --            80/0                                   Q-47 Q-47                                                                               ##STR369##     --            80/0                                   Q-48 Q-48                                                                               ##STR370##                                                                                    ##STR371##    70/10                                 Q-49 Q-49                                                                               ##STR372##     --            80/0                                   Q-50 Q-50                                                                              CH.sub.3                                                                                       ##STR373##    40/40                                 Q-51 Q-51                                                                              CH.sub.2 C.sub.6 H.sub.5                                                                       ##STR374##    65/15                                 Q-52 Q-52                                                                              C.sub.6 H.sub.5                                                                                ##STR375##   72/8                                   Q-53 Q-53                                                                               ##STR376##     --            80/0                                   __________________________________________________________________________

EXAMPLE Q-54-Q-70

The procedures of Example Q-37 were repeated except that themacromonomers (M_(D)) listed in the table 7 were substituted formacromonomer (M-14). Mw of each of resultant polymers (Polymers(Q-54)-(Q-70)) was in the range of 2×10³ to 1×10⁴.

                                      TABLE 7                                     __________________________________________________________________________     ##STR377##                                                                                                                              x/y                Ex-                                                        ratio              am-                                                        by                 ple                                                                              [Q]                                                                              X             a.sub.1 /a.sub.2                                                                      R           Z                  weight             __________________________________________________________________________    Q-54                                                                             Q-54                                                                             COO(CH.sub.2).sub.2 OOC                                                                     H/CH.sub.3                                                                            COOCH.sub.3                                                                                ##STR378##        70/30              Q-55                                                                             Q-55                                                                              ##STR379##   CH.sub.3 /CH.sub.3                                                                    COOCH.sub.2 C.sub.6 H.sub.5                                                                ##STR380##        60/40              Q-56                                                                             Q-56                                                                              ##STR381##   H/CH.sub.3                                                                            COOC.sub.6 H.sub.5                                                                         ##STR382##        65/35              Q-57                                                                             Q-57                                                                              ##STR383##   CH.sub.3 /CH.sub.3                                                                    COOC.sub.2 H.sub.5                                                                         ##STR384##        80/20              Q-58                                                                             Q-58                                                                             COOCH.sub.2 CH.sub.2                                                                        CH.sub.3 /H                                                                           C.sub.6 H.sub.5                                                                            ##STR385##        50/50              Q-59                                                                             Q-59                                                                              ##STR386##   CH.sub.3 /CH.sub.3                                                                    COOC.sub.2 H.sub.5                                                                         ##STR387##        90/10              Q-60                                                                             Q-60                                                                              ##STR388##   H/CH.sub.3                                                                            COOC.sub.3 H.sub.7                                                                         ##STR389##        80/20              Q-61                                                                             Q-61                                                                              ##STR390##   CH.sub.3 /CH.sub.3                                                                    COOC.sub.2 H.sub.5                                                                         ##STR391##        65/35              Q-62                                                                             Q-62                                                                              ##STR392##   CH.sub.3 /H                                                                           COOC.sub.6 H.sub.5                                                                         ##STR393##        70/30              Q-63                                                                             Q-63                                                                              ##STR394##   CH.sub.3 /CH.sub.3                                                                    "                                                                                          ##STR395##        75/25              Q-64                                                                             Q-64                                                                             COOCH.sub.2 CH.sub. 2                                                                       CH.sub.3 /H                                                                           C.sub.6 H.sub.5                                                                            ##STR396##        90/10              Q-65                                                                             Q-65                                                                             CONHCOOCH.sub.2 CH.sub.2                                                                    CH.sub.3 /CH.sub.3                                                                     ##STR397##                                                                                ##STR398##        70/30              Q-66                                                                             Q-66                                                                              ##STR399##   H/CH.sub.3                                                                            COOC.sub.4 H.sub.9                                                                         ##STR400##        80/20              Q-67                                                                             Q-67                                                                             COO           CH.sub.3 /CH.sub.3                                                                    COOCH.sub.3                                                                                ##STR401##        70/30              Q-68                                                                             Q-68                                                                             COO(CH.sub.2 ) .sub.4OOC                                                                    CH.sub.3 /CH.sub.3                                                                     ##STR402##                                                                                ##STR403##        75/25              Q-69                                                                             Q-69                                                                              ##STR404##   H/H     C.sub.6 H.sub.5                                                                            ##STR405##        70/30              Q-70                                                                             Q-70                                                                              ##STR406##   H/CH.sub.3                                                                            COOCH.sub.2 C.sub.6 H.sub.5                                                                ##STR407##        85/15              __________________________________________________________________________

[EXAMPLE 1]

A mixture of 1.5 g of metal-free X-form phthalocyanine (available fromDAINIPPON INK AND CHEMICALS, INC.), 8.5 g of Polymer (R-1) representedby the following formula, 1.5 g of Polymer (Q-5), 0.3 g of Polymer(P-104) of the present invention, 0.15 g of Compound A represented bythe following formula and 80 g of tetrahydrofuran was charged togetherwith glass beads in a 500 ml glass container. The mixture was dispersedby a paint shaker (available from TOYO SEIKI SEISAKUSHO) for 60 minutesand then the glass beads were separated by filtration to prepare adispersion for a photoconductive layer.

The dispersion was coated with a wire bar on a base for a paper masterhaving 0.2 mm thickness subjected to both of a treatment for electricalconductivity and a treatment for solvent resistance. After being driedby air to be tack-free, the coating was dried in a circulating oven at110° C. for 20 seconds and then heated to 140° C. for 1 hour to obtain aphotoconductive layer having 10 μm thickness. ##STR408##

The numbers of the repeating units in the formula represent a ratio byweight. ##STR409##

A thermoplastic resin solution having the following contents was thenprepared to form a transfer layer (or a transfer removable layer or aremovable layer) on the photoconductive layer.

    ______________________________________                                        Poly(vinyl acetate/crotonic acid)                                                                   3 g                                                     (95/5, Mw 5 × 10.sup.4)                                                 28% Aqueous Ammonia   1 g                                                     Ethanol               97 g                                                    ______________________________________                                    

After the above solution was coated with a wire bar on thephotoconductive layer, the coating was dried in an oven at 120° C. for20 seconds to prepare an electrophotographic material for colorproofing, comprising a transfer layer having 1.3 μm thickness.

[Comparative Example A1]

An electrophotographic material for color proofing was prepared in thesame manner as that of Example 1 except that 0.3 g of a random copolymer(RP-1) was used instead of 0.3 g of Polymer (P-104). ##STR410##

[Comparative Example B1]

An electrophotographic material for color proofing was prepared in thesame manner as that of Example 1 except that 10 g of Polymer (R-1) wasused instead of 8.5 g of Polymer (R-1) and 1.5 g of Polymer (Q-1).

[Test Example]

The electrostatic properties, transfer properties and imagereproducibilities of the electrophotographic materials for colorproofing obtained in Example 1 and Comparative Examples A1 and B1 wereevaluated. The results are summarised in Table 8 below.

                  TABLE 8                                                         ______________________________________                                                    Exam- Comparative                                                                              Comparative                                                  ple 1 Example A1 Example B1                                       ______________________________________                                        Electrostatic properties.sup.1)                                               V.sub.10 (-V)                                                                 I (20° C., 65% RH)                                                                   580     570        560                                          II (30° C., 80% RH)                                                                  555     550        515                                          D.R.R (%)                                                                     I (20° C., 65% RH)                                                                   86      85         81                                           II (30° C., 80% RH)                                                                  82      81         72                                           E.sup.1 /2 (erg/cm.sup.2)                                                     I (20° C., 65% RH)                                                                   16      18         22                                           II (30° C., 80% RH)                                                                  18      20         25                                           Transfer property.sup.2)                                                                    ◯                                                                         X          ◯                                              very    severe     very good                                                  good    transfer                                                                      defect                                                  Image reproducibility.sup.3)                                                  I (20° C., 65% RH)                                                                   ◯                                                                         XX         ◯                                              very    severe     very good                                                  good    image                                                                         defect                                                  II (30° C., 80% RH)                                                                  ◯                                                                         XX         X˜Δ                                            very    severe     low density                                                good    image      fine lines and                                                     defect     fine characters                                                               disappeared                                  ______________________________________                                    

The properties shown in Table 8 were evaluated as follows.

1) Electrostatic properties

Each of the electrophotographic materials for color proofing was coronadischarged at -6 kV for 20 seconds by means of a paper analyzer (PaperAnalyzer SP-428, Kawaguchi Electric Co., Ltd.) in a darkroom at 20° C.(65% RH) and left for 10 seconds and the surface potential wasdetermined (V₁₀). Then, the material was further left in dark for 120seconds and again the potential was determined (V₁₃₀) to obtain a darkdecay retention rate (D.R.R.) in %, which means a potential retentionrate after the 120 second-dark decay was allowed, according to theequation, D.R.R. (%)=(V₁₃₀ /V₁₀)×100.

Further, the surface of the photoconductive layer in contact with thetransfer layer was charged by corona discharge to -500 V, then thematerial was irradiated with monocolor light having a wavelength of 780nm, and the time required for 1/2 decay of the surface potential (V₁₀)was determined. Based on the obtained time, exposure, E_(1/2), wascalculated in term of erg/cm².

Also under the condition of the temperature of 30° C. and 80% RH, theproperties were evaluated in the same manner as described above.Hereinafter, the conditions of 20° C., 65% RH and 30° C., 80% RH arereferred to as Conditions I and II respectively.

2) Transfer property

A sheet of coated paper was laid on the electrophotographic materialhaving a transfer layer and then transferred at a speed of 5 mm/secbetween a pair of hollow metal heat rollers coated with a siliconerubber layer and having an infrared lamp heater therein.

The surface temperatures of the rollers, the upper one and the lowerone, were maintained at 120° C., the rollers were arranged so as toobtain the nip pressure of 5 kgf/cm², and the conveyor speed wascontrolled at 5 mm/sec.

After being cooled to room temperature as the coated paper was laid onthe material, the paper was separated from the electrophotographicmaterial. The quality of the image transferred to the coated paper wasvisually evaluated.

3) Image reproducibility

An image was formed on each of the electrophotographic materials forcolor proofing under the conditions, Condition (I) or (II), and theimage reproducibility of the color proof after the transfer wasevaluated.

Each of the electrophotographic materials was charged by coronadischarge to +450 volts in dark. The charged electrophotographicmaterial was imagewise exposed to light by a Ga--Al--As semiconductorlaser (oscillation wavelength 780 nm) having 5 mW of output power with30 erg/cm³ of irradiation measured on the electrophotographic materialin a pitch of 25 μm at a scanning speed of 300 cm/sec in a mode ofnegative mirror image, based on the information about yellow color amonginformations about yellow, magenta, cyan and black, which were recordedin a harddisk of a color scanner system as digital image data which wereobtained by reading an original using the color scanner system andconducting color separation and correction regarding some colorreproductions specific to the system. Subsequently, the exposedelectrophotographic material was reversally developed using a yellowliquid developer for a signature system (available from Eastman Kodak)75-fold (by weight) diluted with Isoper H (available from Esso StandardOil Co.) by a developing apparatus having a pair of plane developingelectrodes under the application of +400 volts of bias voltage toelectrically deposit toners on the exposed areas of theelectrophotographic material and then the developed electrophotographicmaterial was rinsed in a bath of Isoper H to remove contamination in thenon-image areas.

The above procedure was repeated using each information of magenta, cyanand black instead of the information of yellow.

The image formed on the obtained electrophotographic material afterimage-form production was fixed using a heat roller.

Subsequently, coated paper (regular printing paper) was laid on theelectrophotographic material having fixed image and then transferred ata speed of 10 mm/sec between a pair of rubber rollers which were incontact each other under a pressure of 15 kgf/cm² and whose surfaceswere constantly maintained at 120° C.

After being cooled to room temperature, the coated paper was separatedfrom the electrophotographic material. Image formed on the coated paperwas visually evaluated regarding fog and image quality.

As shown in Table 8, the materials of Example 1 (the present invention)and Comparative Example A1 showed good electrostatic propertiesregardless of the variation of the conditions.

However, the electrostatic properties, especially the dark decayretention rate (D.R.R.) and the photosensitivity (E_(1/2)), of thematerial obtained in Comparative Example B1, which comprised only theconventional polymer as the binder resin, were deteriorated.

It is considered that the above difference is due to the fact that, inthe electrophotographic material for color proofing of the presentinvention, the polymer (Q) sufficiently adsorb the photoconductivecompound and enables uniform dispersion of the photoconductive compoundand thereby ensures a condition which allows the sufficient and uniforminteraction between the chemical sensitizer, Compound (A), and thephotoconductive compound.

Further, the transfer layers of the materials obtained in Example 1 andComparative Example B1, which utilises the polymer (Q) of the presentinvention, were completely transferred to the receptive materials,whereas the material for color proofing of Comparative Example A1 couldnot successfully peeled off from the coated paper and the transfer layeror the photoconductive layer was broken.

It is considered that the above difference is due to the fact that, inthe electrophotographic material for color proofing of the presentinvention and. Comparative Example B1, the polymer (P), which is thefluorine atom-containing copolymer, in the photoconductive layermigrates and is concentrated on the surface of the layer at the time ofthe formation of the photoconductive layer and then forms a cured filmthrough chemical bondings between the polymer chains by a crosslinkingagent to form a definite interface of the layers, whereas such adefinite interface is not formed in the material of Comparative ExampleA1, which utilizes a conventional random copolymer.

In addition, the electrophotographic material for color proofing of thepresent invention could provide the color proof with a good color imageregardless of the change of environmental conditions, while the materialof Comparative Example A1 could not provide a sufficient image becauseof the bad transfer property and the of the material of ComparativeExample B1 resulted in extremely deteriorated image reproducibilityunder high humidity.

Further, the peeling property of the photoconductive layers formed inExample 1 and Comparative Example A1 were examined by determining tackstrength of these photoconductive layers according to JISZ0237-1980,"Adhesion Tape or Sheet Test Method" before the formation of thetransfer layer. As a result, tack strength of the photoconductive layerof 6 g.f for the material of Example 1 and 330 g.f for the material ofComparative Example A1 were obtained.

As described above, the electrophotographic material for color proofingof the present invention alone showed excellent properties.

[EXAMPLE 2]

A mixture of 200 g of photoconductive zinc oxide, 10 g of Polymer (Q-2),40 g of Polymer (R-2) represented by the following formula, 8 g ofPolymer (P-103) of the present invention, 0.018 g of Dye (D-1)represented by the following formula, 0.20 g of N-hydroxysuccinimide and300 g of toluene was charged in a homogenizer (Nihon Seiki Co.,Ltd.) anddispersed for 10 minutes at 9×10³ rpm.

To this dispersion, 0.3 g of phthalic anhydride and 0.01 g ofo-chlorophenol were added and dispersed for 1 minute at 1×10³ rpm.

The dispersion was coated with a wire bar on a base for a paper masterhaving 0.2 mm thickness subjected to both of a treatment for electricalconductivity and a treatment for solvent resistance. After being driedby air to be tack-free, the coating was dried in a circulating oven at90° C. for an hour to obtain a photosensitive layer having 15 μmthickness. ##STR411##

The same thermoplastic resin solution as that of Example 1 was prepared,coated on the photosensitive layer and dried to form a transfer layer onthe photosensitive layer.

[Comparative Example C1]

An electrophotographic material for color proofing was prepared in thesame manner as that of Example 2 except that 50 g of Polymer (R-2) alonewas used instead of 10 g of Polymer (Q-2) and 40 g of Polymer (R-2).

[Test Example]

Smoothnesses, electrostatic properties, transfer properties and imagereproducibilities of the electrophotographic materials for colorproofing obtained in Example 2 and Comparative-Example C1 wereevaluated.

The results are summarised in Table 9 below.

                  TABLE 9                                                         ______________________________________                                                              Comparative                                                          Example 2                                                                              Example C1                                              ______________________________________                                        Smoothness of the surface.sup.1)                                                             1,100      1,050                                               of the photoconductive                                                        layer                                                                         Electrostatic Properties                                                      V.sub.10 (-V)                                                                 I              710        550                                                 II             685        510                                                 D.R.R. (%)                                                                    I              88         75                                                  II             85         46                                                  E.sup.1 /2 (erg/cm.sup.2)                                                     I              10         25                                                  II             12         26                                                  Transfer property                                                                            ◯                                                                            ◯                                                      very good  very good                                           Reproducibility.sup.2)                                                        of image                                                                      I              ◯                                                                            Δ˜◯                                        good       a little bit low density                                                      fine lines and fine                                                           characters slightly                                                           disappeared                                         II             ◯                                                                            XX                                                                 good       low density                                                                   background contamination                                                      fine lines and fine                                                           characters disappeared                              ______________________________________                                    

As to the properties shown in Table 9, the electrostatic properties andthe transfer properties were evaluated in the same manner as in Example1, and the smoothness and the image reproducibility were evaluated asfollows.

1) Smoothness of Photoconductive Layer

The smoothness of the electrophotographic materials for color proofing(see/cc) was determined by a Beck smoothness tester (Kumagaya RikohCo.,Ltd.) under the condition of 1 cc air volume.

2) Image Reproducibility

Each of the electrophotographic materials was charged by coronadischarge to -600 volts in dark. The charged electrophotographicmaterial was imagewise exposed to light by a semiconductor laser(oscillation wavelength 780 nm) with 25 erg/cm³ of irradiation measuredon the surface of the electrophotographic material in a mode of positivemirror image, based on the information about yellow color. The residualvoltage on the exposed areas was -120 volts. Subsequently, the exposedelectrophotographic material was positively developed using a yellowtoner for VERSATECK 3000 (color electrostatic plotter available fromXerox Co.) diluted with a 50-fold amount of Isoper H by a developingapparatus having a pair of plane developing electrodes under theapplication of -200 volts of bias voltage to electrically deposit tonerson the unexposed areas of the electrophotographic material and then thedeveloped electrophotographic material was rinsed in a bath of Isoper Hto remove background contamination in the non-image areas.

The above procedure was repeated using each information of magenta, cyanand black instead of the information of yellow.

Subsequently, coated paper was laid on the electrophotographic materialdeveloped with the four color toners and then transferred at a speed of6 mm/sec between a pair of rubber rollers which were in contact eachother under a pressure of 10 kgf/cm² and whose surfaces were constantlymaintained at 120° C.

After being cooled to room temperature, the coated paper was separatedfrom the electrophotographic material.

As shown in Table 9, the material of Example 2 (the present invention)showed extremely excellent electrostatic properties and when theenvironmental conditions were changed, the fluctuation of the propertieswas not so significant. Further, in the practical image formation withthis material of the invention, good image reproducibility was obtainedas to fine images such as fine lines and fine characters withoutbackground contamination. On the other hand, the electrostaticproperties of the material obtained in Comparative Example C1 wereextremely deteriorated, especially under a high humidity, andpractically acceptable image reproducibility was not obtained with thiscomparative material. That is, the fog of non-imaged areas and the imagedensity were deteriorated and the disappearance of fine lines becamesignificant.

Good transfer properties were obtained in both of the materials, andthus it was found that the peeling properties of the photoconductivelayer may be improved by the polymer (P) not only in the photoconductivelayer comprising the organic photoconductive compound but also in thelayer comprising the inorganic photoconductive compound.

Further, the peeling property of the photoconductive layers formed inExample 2 and Comparative Example C1 were examined by determining tackstrength of these photoconductive layers according to JISZ0237-980,"Adhesion Tape or. Sheet Test Method" before the formation of thetransfer layer. As a result, tack strength of the photoconductive layerof 8 g.f for the material of Example 2 and more than 400 g.f for thematerial of Comparative Example C1 were obtained.

As described above, the electrophotographic material for color proofingof Example 2 showed good transfer property and showed good imagereproducibility regardless of the change of the environmentalconditions.

[EXAMPLE 3]

5 g of 4,4'-bis(diethylamino)-2,2'-dimethyl triphenylmethane as anorganic photoconductive compound, 1 g of Polymer (Q-32), 3 g of Polymer(R-3) represented by the following formula, 0.8 g of Polymer (P-119) ofthe present invention, 40 mg of Dye (D-2) represented by the followingformula and 0.20 g of an anilide compound (B) represented by thefollowing formula as a chemical sensitizer were dissolved in a mixtureof 30 ml of methylene chloride and 30 ml of ethylene chloride to preparea solution for a photoconductive layer.

The solution was coated with a wire-round rod on anelectrically-conductive transparent substrate which comprises apolyethylene terephthalate substrate (100 μm in thickness) having anindium oxide film deposited thereon and has a surface resistance of 10³Ω to form a photoconductive layer having about 4 μm thickness.##STR412##

The results obtained in an adhesion test with an adhesive-backed tape,which was carried out to confirm the partial presence of the polymer (P)at the surface of the photoconductive layer, revealed that the adhesionof the photoconductive layer of the material of the invention wasone-seventieth compared with a photoconductive layer formed in the samemanner as in Example 3 except that Polymer (R-3) was used instead ofPolymer (P-119) in the same amount.

The same thermoplastic resin solution as that of Example 1 was prepared,coated on the photoconductive layer and dried to form a transfer layeron the photoconductive layer.

An adhesive-backed tape was attached to the surface of the removablelayer and peeled off. As a result, only the transfer layer was easilyseparated from the photosensitive layer.

The image quality and the transfer properties of the electrophotographicmaterial thus obtained were evaluated in the same manner as that ofExample 1 except that a He--Ne laser having an oscillation wavelength of630 nm was used instead of the semiconductor laser having an oscillationwavelength of 780 nm.

A clear color copy image without fog was obtained on coated paper aftertransfer. The image had sufficient strength.

[EXAMPLE 4]

A mixture of 5 g of bis-azo pigment represented by the followingformula, 95 g of tetrahydrofuran, 1.5 g of Polymer (Q-17) and a solutionof 3.5 g of polyester resin, Byron 200 (available from TOYOBO CO., LTD)and 30 g of tetrahydrofuran was sufficiently ground in a ball mill.Then, the mixture was drawn and 520 g of tetrahydrofuran were addedthereto while stirring. The obtained dispersion was coated with awire-wound rod on the same electrically-conductive transparent substrateas that used in Example 1 to form a charge generation layer having about0.7 μm thickness. ##STR413##

Subsequently, a solution consisting of 20 g of a hydrazone compoundrepresented by the following formula, 2 g of Polymer (P-102), 20 g ofpolycarbonate resin Lexan 121 (available from GE Co.), 0.04 g ofisophorone diisocyanate, 0.001 g of tetrabutoxy titanate and 160 g oftetrahydrofuran was coated with a wire-wound rod on the chargegeneration layer, dried at 60° C. for 30 seconds, and heated at 120° C.for 1 hour to form a charge transport layer having thickness of about 18μm. Thus, the obtained electrophotographic material comprising the twofunctional layers of the charge generation layer and the chargetransport layer. ##STR414##

The same thermoplastic resin solution as that of Example 1 was prepared,coated on the photoconductive layer and dried to form a transfer layeron the photoconductive layer.

An adhesive-backed tape was attached to the surface of the transferlayer and peeled off. As a result, only the transfer layer was easilyseparated from the photoconductive layer.

The image quality and the transfer properties of the electrophotographicmaterial thus obtained were evaluated in the same manner as that ofExample 1 except that a He--Ne laser having an oscillation wavelength of630 nm was used instead of the semiconductor laser having an oscillationwavelength of 780 nm.

A clear color copy image without fog was obtained on coated paper aftertransfer. The image had sufficient strength.

[EXAMPLES 5 to 7]

Electrophotographic materials for color proofing were prepared in thesame manner as that of Example 1 except that 0.3 g of Polymer (P) inTable 7 was used instead of 0.3 g of Polymer (P-104).

The electrostatic properties, transfer properties and imagereproducibilities of the resultant electrophotographic materials forcolor proofing were evaluated in the same manners as those of Example 1.The results are summarised in Table 10 below.

                  TABLE 10                                                        ______________________________________                                        Examples      Example 5 Example 6  Example 7                                  ______________________________________                                        Polymer (P)   (P-209)   (P-308)    (P-421)                                    Electrostatic properties                                                      V.sub.10 (-V)                                                                 I             580       585        580                                        II            560       560        565                                        D.R.R. (%)                                                                    I             87        86         86                                         II            83        84         82                                         E.sup.1 /10 (erg/cm.sup.2)                                                    I             16        15         17                                         II            17        18         20                                         Transfer property                                                                           ◯                                                                           ◯                                                                            ◯                                            very good very good  very good                                  Image reproducibility                                                         I             ◯                                                                           ◯                                                                            ◯                                            good      good       good                                       II            ◯                                                                           ◯                                                                            ◯                                            good      good       good                                       ______________________________________                                    

As shown in Table 10, all of the materials of Examples 5 to 7 showedgood electrostatic properties, transfer properties and imagereproducibilities at levels comparable to those of the material obtainedin Example 1.

Tack strength of each of the materials of Examples 5 to 7 was in therange of 5 to 8 g.f. Namely, they showed a good peeling property.

The electrophotographic material prepared in the same manner as inExample 1 except that Polymer (R-1) was used instead of Polymer (P-104)in the same amount showed inferior transfer property. Namely, thephotoconductive layer of the material could not be successfully peeledoff from the transfer layer.

The electrophotographic materials for color proofing were prepared inthe same manner as that of Example 1 except that 10 g of Polymer (R-1)was used instead of 8.5 g of Polymer (R-1) and 1.5 g of Polymer (Q-5),and each of the polymers (P) used in Examples 5 to 7 was used instead ofPolymer (P-104). The electrostatic properties of the resultantelectrophotographic materials were extremely deteriorated whenenvironmental conditions were changed, especially to a high temperatureand a high humidity, and practically acceptable image reproducibilitywas not obtained with the materials. That is, the fog of non-imagedareas and the image density were deteriorated and the disappearance offine lines and fine characters became significant.

Accordingly, the results of the above test examples showed that theelectrophotographic materials of the present invention can provideextremely excellent color proofs.

[EXAMPLES 8 to 27]

Electrophotographic materials for color proofing were prepared in thesame manner as that of Example 1 except that 1.5 g of Polymer (Q) shownin Table 11 was used instead of 1.5 g of Polymer (Q-5).

                  TABLE 11                                                        ______________________________________                                        Example  Polymer(Q)   Example  Polymer(Q)                                     ______________________________________                                         8       Q-1          18       Q-23                                            9       Q-3          19       Q-29                                           10       Q-6          20       Q-33                                           11       Q-9          21       Q-40                                           12       Q-11         22       Q-46                                           13       Q-13         23       Q-52                                           14       Q-16         24       Q-59                                           15       Q-18         25       Q-65                                           16       Q-20         26       Q-68                                           17       Q-22         27       Q-70                                           ______________________________________                                    

The image quality and the transfer properties of each of theelectrophotographic materials thus obtained were evaluated in dark inthe same manner as that of Example 1. Clear color copy images withoutbackground contamination were obtained on coated paper after transfer.The images had sufficient strength.

[EXAMPLES 28 to 50]

Electrophotographic materials for color proofing were prepared in thesame manner as that of Example 1 except that 1.5 g of Polymer (Q), 0.3 gof Polymer (P) and cross-linking compounds shown in Table 12 were usedinstead of 1.5 g of Polymer (Q-5), 0.3 g of Polymer (P-104) and thecross-linking compound used in Example 1.

                  TABLE 12                                                        ______________________________________                                              Poly-   Poly-                                                           Exam- mer     mer                                                             ple   (Q)     (P)      Cross-linking compound                                 ______________________________________                                        28    Q-2     P-202    gluconic anhydride                                                                            0.15 g                                                        o-cresol        0.01 g                                 29    Q-4     P-301    gluconic anhydride                                                                            0.15 g                                                        o-cresol        0.01 g                                 30    Q-7     P-214    ethylene glycol 0.03 g                                                        diglycidyl ether                                                              zinc stearate   0.001 g                                31    Q-10    P-315    ethylene glycol 0.03 g                                                        diglycidyl ether                                                              zinc stearate   0.001 g                                32    Q-17    P-419    ethylene glycol 0.03 g                                                        diglycidyl ether                                                              zinc stearate   0.001 g                                33    Q-19    P-207    1,6-dihexanediamine                                                                           0.20 g                                 34    Q-21    P-423    gluconic acid   0.18 g                                                        phenol          0.002 g                                35    Q-30    P-421    phthalic anhydride                                                                            0.2 g                                                         o-chlorophenol  0.001 g                                36    Q-25    P-210    3-aminopropyltrimethoxy                                                                       0.1 g                                                         silane                                                 37    Q-24    P-321    3-aminopropyltrimethoxy                                                                       0.1 g                                                         silane                                                 38    Q-35    P-417    3-aminopropyltrimethoxy                                                                       0.1 g                                                         silane                                                 39    Q-41    P-212    propylene glycol                                                                              0.8 g                                                         tetrabutoxytitanate                                                                           0.001 g                                40    Q-45    P-323    propylene glycol                                                                              0.8 g                                                         tetrabutoxytitanate                                                                           0.001 g                                41    Q-48    P-213    trimethylolpropane                                                                            1.0 g                                                         tin dilaurate dibutoxide                                                                      0.001 g                                42    Q-49    P-125    trimethylolpropane                                                                            1.0 g                                                         tin dilaurate dibutoxide                                                                      0.001 g                                43    Q-50    P-215    phthalic anhydride                                                                            0.3 g                                                         cobalt acetylacetonate                                                                        0.001 g                                44    Q-55    P-329    phthalic anhydride                                                                            0.3 g                                                         cobalt acetylacetonate                                                                        0.001 g                                45    Q-56    P-421    phthalic anhydride                                                                            0.3 g                                                         cobalt acetylacetonate                                                                        0.001 g                                46    Q-58    P-322    propylene glycol                                                                              0.05 g                                                        diglycidyl ether                                                              o-chlorophenol  0.002 g                                47    Q-60    P-222    ROOCNH(CH.sub.2).sub.6 NHCOOR                                                                 0.2 g                                                         tetrapropoxytitanate                                                                          0.001 g                                48    Q-64    P-122    ROOCNH(CH.sub.2).sub.6 NHCOOR                                                                 0.2 g                                                         tetrapropoxytitanate                                                                          0.001 g                                49    Q-66    P-335    γ-glycidepropyl                                                                         0.1 g                                                         trimethoxysilane                                       50    Q-67    P-118    γ-glycidepropyl                                                                         0.1 g                                                         trimethoxysilane                                       ______________________________________                                    

In Table 12, R represents an m-methylphenyl group.

The image quality and the transfer properties of each of theelectrophotographic material thus obtained were evaluated in the samemanner as that of Example 1.

Clear color copy images without background contamination were obtainedon coated paper after transfer. The images had sufficient strength.

[EXAMPLES 51 to 58]

Electrophotographic materials for color proofing were prepared in thesame manner as that of Example 1 except that 2 g of Polymer (Q), 9 g ofPolymer (R) and 0.3 g of Polymer (P) were used.

                                      TABLE 13                                    __________________________________________________________________________         Polymer                                                                            Polymer                                                                            Polymer                                                        Example                                                                            (Q)  (R)  (P)  Cross-linking compound                                    __________________________________________________________________________    51   Q-8  R-4  P-429                                                                              benzoyl peroxide                                                                             0.008                                                                            g                                       52   Q-12 R-5  P-116                                                                              1,4-butanediol 0.3                                                                              g                                                           tin dilaurate dibutoxide                                                                     0.001                                                                            g                                       53   Q-28 R-6  P-428                                                                              ethyleneglycol dimethacrylate                                                                2.0                                                                              g                                                           2,2'-azobis(isovalero nytrile)                                                               0.03                                                                             g                                       54   Q-34 R-6  P-325                                                                              ethyleneglycol dimethacrylate                                                                2.0                                                                              g                                                           2,2'-azobis(isovalero nytrile)                                                               0.03                                                                             g                                       55   Q-35 R-7  P-129                                                                              divinyl adipate                                                                              2.2                                                                              g                                                           2,2'-azobis(isovalero nytrile)                                                               0.01                                                                             g                                       56   Q-38 R-7  P-336                                                                              divinyl adipate                                                                              2.2                                                                              g                                                           2,2'-azobis(isovalero nytrile)                                                               0.01                                                                             g                                       57   Q-50 R-8  P-422                                                                              block isocyanate                                                                             3  g                                                           Aditol VXL 81                                                                 (manufactured by Hoechst)                                                     butyl titanate dimer                                                                         0.02                                                                             g                                       58   Q-56 R-8  P-126                                                                              block isocyanate                                                                             3  g                                                           Aditol VXL 81                                                                 (manufactured by Hoechst)                                                     butyl titanate dimer                                                                         0.02                                                                             g                                       __________________________________________________________________________    Polymers (R-4) to (R-8) are represented by the following formulae.            (R-4)                                                                          ##STR415##                                                                   (R-5)                                                                          ##STR416##                                                                   (R-6)                                                                          ##STR417##                                                                   (R-7)                                                                          ##STR418##                                                                   (R-8)                                                                          ##STR419##                                                                   Transfer layers were formed on the above-obtained photoconductive layers      in the same manner as that of Example 1 to obtain electrophotographic         materials for color proofing. When color proofs were prepared by using        these materials, clear copy images were obtained without background       

Electrophotographic materials for color proofing were prepared in thesame manner as that of Example 1 except that polymers and solvents shownin Table 14 were used instead of poly(vinyl acetate/crotonic acid)(95/5,ratio by weight).

                  TABLE 14                                                        ______________________________________                                        Exam-                       Solvent for                                       ple   Thermoplastic resins  Coating                                           ______________________________________                                        59    Cellulose acetate butyrate:                                                                         Ethyl acetate                                           Cellidor Bsp                                                                  (manufactured by Bayer AG)                                              60    Polyvinyl butyral resin: ESLECK                                                                     Ethanol                                                 (manufactured by Sekisui                                                      Chemical Co.,Ltd)                                                       61    Cellulose propionate: Ethyl acetate                                           CELLIDORIA (manufactured                                                      by DAICEL CHEMICAL                                                            INDUSTRIES, LTD)                                                        62    Poly(vinyl acetate)   Methyl ethyl                                                                  ketone                                            63    Poly(vinyl acetate/crotonic acid)                                                                   Ethanol solution                                        (molar ratio 95/5) and                                                                              containing                                              Cellidor Bsp (ratio by weight 8/2)                                                                  1% Aqueous                                                                    Ammonia                                           64    Methylmethacrylate/   Tetrahydrofuran                                         methylacrylate copolymer                                                      (ratio by weight 6/4)                                                   65    Styrene/butadiene copolymer                                                                         Toluene                                                 (Sorprene 1205)                                                               (manufactured by Asahi Chemical                                               Industry Co.,Ltd.)                                                      66    Poly(vinyl acetate)/  Methylethyl-                                            poly(ethylmethacrylate)                                                                             ketone                                                  (ratio by weight 6/4)                                                   ______________________________________                                    

Electrostatic properties, transfer properties and imagereproducibilities of the obtained materials were evaluated in the samemanners as those of Example 1. All of the materials showed thoseproperties at levels comparable to those of the material obtained inExample 1.

What is claimed is:
 1. An electrophotographic material for colorproofing which comprises a substrate, a photoconductive layer and atransfer layer in this order, and is used for preparing a color proof ina process wherein at least one color toner image iselectrophotographically formed on the transfer layer and thentransferred together with said transfer layer to a sheet material toprepare the color proof, wherein said photoconductive layer comprises apolymer (P) selected from the group consisting of the following polymers(P₁), (P₂), (P₃) and (P₄); a polymer (Q) selected from the groupconsisting of the following polymers (Q₁) and (Q₂); and a polymer (R)containing at least one unit having photo and/or thermosettinggroup(s),the polymer (P) is present at least in the region near thesurface facing said transfer layer, the polymer (P) comprises at leastone polymer segment (X) containing not less than 50% by weight of unitshaving fluorine atom(s) and/or silicon atom(s) and at least one polymersegment (Y) containing units having photosetting and/or thermosettinggroup(s), wherein segment (X) is oriented toward the transfer layer andsegment (Y) is oriented toward the inside of the photoconductive layer,and the surface of said photoconductive layer which contacts with thetransfer layer has tack strength of not more than 150 gram.force, whichis measured by Pressure Sensitive Tape and Sheet Test of JISZ0237-1980,the polymer (P1): a linear block copolymer which contains atleast one polymer segment (X) containing not less than 50% by weight ofunits having fluorine atom(s) and/or silicon atom(s) and at least onepolymer segment (Y) containing units having photosetting and/orthermosetting group(s);the polymer (P₂) a star type copolymer whichcontains at least three AB type block copolymer chains consisting of apolymer segment (X) containing not less than 50% by weight of unitshaving fluorine atom(s) and/or silicon atom(s) and a polymer segment (Y)containing units having photosetting and/or thermosetting group(s), andsaid block copolymer chains are bonded through an organic group;thepolymer (P₃): a graft copolymer which contains at least one polymersegment (X) containing not less than 50% by weight of units havingfluorine atom(s) and/or silicon atom(s) and at least one polymer segment(Y) containing units having photosetting and/or thermosettinggroup(s);the polymer (P₄): an AB type or ABA type block copolymer whichcontains at least one polymer segment (X) containing not less than 50%by weight of units having fluorine atom(s) and/or silicon atom(s) and atleast one polymer segment (Y) containing units having photosettingand/or thermosetting group(s), wherein at least one said polymer segment(X) is the following graft type polymer segment (X'), at least one saidpolymer segment (Y) is the following graft type polymer segment (Y'), orat least one said polymer segment (X) is the following graft typepolymer segment (X') and at least one said polymer segment (Y) is thefollowing graft type polymer segment (Y'):the graft type polymer segment(X'): a polymer segment which has a weight-average molecular weight of1×10³ ˜2×10⁴, and contains at least one macromonomer segment (M_(A))which contains not less than 50% by weight of units having fluorineatom(s) and/or silicon atom(s); the graft type polymer segment (Y'): apolymer segment which has a weight-average molecular weight of 1×10³˜2×10⁴, and contains at least one macromonomer segment (M_(B)) whichdoes not contain units having fluorine atom(s) and/or siliconatom(s);the polymer (Q₁): a graft type copolymer having a weight-averagemolecular weight of 1×10³ ˜2×10⁴ which is obtained by polymerizing atleast one monomer represented by the formula (I): ##STR420## wherein b¹and b² each represents independently a hydrogen atom, a halogen atom, acyano group or a hydrocarbon group and R³ represents a hydrocarbongroup; and at least one monofunctional macromonomer (M_(C)) having aweight-average molecular weight of not more than 1×10⁴, which containsone or more units having at least one polar group selected from thegroup consisting of --PO₃ H₂, --SO₃ H, --COOH, --PO(OH)R¹ (R¹ is ahydrocarbon group or --OR₂ (R² is a hydrocarbon group)) and a residue ofa cyclic anhydride in its main chain and contains a group havingpolymerizable double bond represented by the formula (II): ##STR421##wherein V¹ represents --COO--, --OCO--, --CH₂ OCO--, --CH₂ COO--, --O--,--SO₂ --, CO--, --CONHCOO--, --CONHCONH--, --CONHSO₂, --, --CON(T¹)--,--SO₂ N(T¹)-- or --C₆ H₅ -- wherein T¹ represents a hydrogen atom or ahydrocarbon group, and b³ and b⁴ each represents independently ahydrogen atom, a halogen atom, a cyano group, a hydrocarbon group,--COOZ¹ or --Z² --COOZ¹ wherein Z¹ represents a hydrogen atom or ahydrocarbon group and Z² represents a hydrocarbon group, in only one endof the main chain;the polymer (Q₂): a graft type copolymer having aweight-average molecular weight of 1×10³ ˜2×10⁴ which contains at leastone unit corresponding to monofunctional macromonomer (M_(D)) which is aAB block copolymer composed of A and B blocks and contains apolymerizable double bond at end of B block, wherein A block contains atleast one unit having at least one polar group selected from the groupconsisting of --PO₃ H₂, --SO₃ H, --COOH, phenolic hydroxyl group,--PO(OH)R¹ (R¹ has the sane meaning as defined in formula (I)) and aresidue of a cyclic anhydride and B block contains at least one unitrepresented by the formula (III): ##STR422## wherein V² represents--COO--, --OCO--, --(CH₂)_(a), OCO--, (CH₂) COO-- (a is an integer of 1to 3), --O--, SO₂ --CO--, --CON(T¹)--, --SO₂ N(T¹)--, --CONHCOO--,--CONHCONH-- or --C₆ H₅ -- (T¹ has the same meaning as defined informula (II)), R⁴ represents a hydrogen atom or a hydrocarbon group andb⁵ and b⁶ each has independently the same meaning as b¹ or b².
 2. Theelectrophotographic material for color proofing of claim 1 wherein saidpolymer (P) is the polymer (P₁), and said polymer (Q) is the polymer(Q₁).
 3. The electrophotographic material for color proofing of claim 1wherein said polymer (P) is the polymer (P₂), and said polymer (Q) isthe polymer (Q₁).
 4. The electrophotographic material for color proofingof claim 1 wherein said polymer (P) is the polymer (P₃), and saidpolymer (Q) is the polymer (Q₁).
 5. The electrophotographic material forcolor proofing of claim 1 wherein said polymer (P) is the polymer (P₄),and said polymer (Q) is the polymer (Q₁).
 6. The electrophotographicmaterial for color proofing of claim 1 wherein said polymer (P) is thepolymer (P₁), and said polymer (Q) is the polymer (Q₂).
 7. Theelectrophotographic material for color proofing of claim 1 wherein saidpolymer (P) is the polymer (P₂), and said polymer (Q) is the polymer(Q₂).
 8. The electrophotographic material for color proofing of claim 1wherein said polymer (P) is the polymer (P₃), and said polymer (Q) isthe polymer (Q₂).
 9. The electrophotographic material for color proofingof claim 1 wherein said polymer (P) is the polymer (P₄), and saidpolymer (Q) is the polymer (Q₂).
 10. The electrophotographic materialfor color proofing of claim 1 wherein said polymer (P) is contained in alayer which contacts with the transfer layer in an amount of 1 to 30% byweight based on the total weight of the layer.
 11. Theelectrophotographic material for color proofing of claim 1 wherein, saidphotoconductive layer contains a photoconductive compound and saidpolymer (Q) is contained in said photoconductive layer in an amount of 1to 100 parts per 100 parts by weight of the photoconductive compound.12. The electrophotographic material for color proofing of claim 1wherein said polymer (R) is contained in a layer which contacts with thetransfer layer in an amount of 5 to 99.1% by weight based on the totalweight of the layer.
 13. A process for forming a color proof wherein atleast one color toner image is electrophotographically formed on anelectrophotographic material for color proofing which comprises asubstrate, a photoconductive layer and a transfer layer in this order,and then transferred together with said transfer layer to a sheetmaterial to prepare the color proof, wherein said photoconductive layercomprises a polymer (P) selected from the group consisting of thefollowing polymers (P₁), (P₂), (P₃) and (P₄); a polymer (Q) selectedfrom the group consisting of the following polymers (Q₁) and (Q₂); and apolymer (R) containing at least one unit having photo and/orthermosetting group(s),the polymer (P) is present at least in the regionnear the surface facing said transfer layer, the polymer (P) comprisesat least one polymer segment (X) containing not less than 50% by weightof units having fluorine atom(s) and/or silicon atom(s) and at least onepolymer segment (Y) containing units having photosetting and/orthermosetting group(s), wherein segment (X) is oriented toward thetransfer layer and segment (Y) is oriented toward the inside of thephotoconductive layer, and the surface of said photoconductive layerwhich contacts with the transfer layer has tack strength of not morethan 150 gram.force, which is measured by Pressure Sensitive Tape andSheet Test of JIS Z0237-1980,the polymer (P1): a linear block copolymerwhich contains at least one polymer segment (X) containing not less than50% by weight of units having fluorine atom(s) and/or silicon atom(s)and at least one polymer segment (Y) containing units havingphotosetting and/or thermosetting group(s);the polymer (P₂): a star typecopolymer which contains at least three AB type block copolymer chainsconsisting of a polymer segment (X) containing not less than 50% byweight of units having fluorine atom(s) and/or silicon atom(s) and apolymer segment (Y) containing units having photosetting and/orthermosetting group(s), and said block copolymer chains are bondedthrough an organic group;the polymer (P₃): a graft copolymer whichcontains at least one polymer segment (X) containing not less than 50%by weight of units having fluorine atom(s) and/or silicon atom(s) and atleast one polymer segment (Y) containing units having photosettingand/or thermosetting group(s);the polymer (P₄): an AB type or ABA typeblock copolymer which contains at least one polymer segment (X)containing not less than 50% by weight of units having fluorine atom(s)and/or silicon atom(s) and at least one polymer segment (Y) containingunits having photosetting and/or thermosetting group(s), wherein atleast one said polymer segment (X) is the following graft type polymersegment (X'), at least one said polymer segment (Y) is the followinggraft type polymer segment (Y'), or at least one said polymer segment(X) is the following graft type polymer segment (X') and at least onesaid polymer segment (Y) is the following graft type polymer segment(Y'):the graft type polymer segment (X'): a polymer segment which has aweight-average molecular weight of 1×10³ ˜2×10⁴, and contains at leastone macromonomer segment (M_(A) ) which contains not less than 50% byweight of units having fluorine atom(s) and/or silicon atom(s); thegraft type polymer segment (Y'): a polymer segment which has aweight-average molecular weight of 1×10³ ˜2×10⁴, and contains at leastone macromonomer segment (M_(B)) which does not contain units havingfluorine atom(s) and/or silicon atom(s);the polymer (Q₁): a graft typecopolymer having a weight-average molecular weight of 1×10³ ˜2×10⁴ whichis obtained by polymerizing at least one monomer represented by theformula (I): ##STR423## wherein b¹ and b² each represents independentlya hydrogen atom, a halogen atom, a cyano group or a hydrocarbon groupand R³ represents a hydrocarbon group; and at least one monofunctionalmacromonomer (M_(C)) having a weight-average molecular weight of notmore than 1×10⁴, which contains one or more units having at least onepolar group selected from the group consisting of --PO₃ H₂, --SO₃ H,--COOH, --PO(OH)R¹ (R¹ is a hydrocarbon group or --OR₂ (R² is ahydrocarbon group)) and a residue of a cyclic anhydride in its mainchain and contains a group having polymerizable double bond representedby the formula (II): ##STR424## wherein V¹ represents --COO--, --OCO--,--CH₂ OCO--, --CH₂ COO--, --O--, --SO₂ --, --CO--, --CONHCOO--,--CONHCONH--, --CONHSO₂ --, --CON(T¹)--, --SO₂ N(T¹)-- or --C₄ H₅ --wherein T¹ represents a hydrogen atom or a hydrocarbon group, and b³ andb⁴ each represents independently a hydrogen atom, a halogen atom, acyano group, a hydrocarbon a group, --COOZ¹ or --Z² --COOZ¹ wherein Z¹represents a hydrogen atom or a hydrocarbon group and Z² represents ahydrocarbon group, in only one end of the main chain;the polymer (Q²): agraft type copolymer having a weight-average molecular weight of 1×10²˜2×10⁴ which contains at least one unit corresponding to monofunctionalmacromonomer (M_(D)) which is a AB block copolymer composed of A and Bblocks and contains a polymerizable double bond at end of B block,wherein A block contains at least one unit having at least one polargroup selected from the group consisting of --PO₃ H₂, --SO₃ H, --COOH,phenolic hydroxyl group, --PO(OH)R¹ (R¹ has the same meaning as definedin formula (I)) and a residue of a cyclic anhydride and B block containsat least one unit represented by the formula (III): ##STR425## whereinV² represents --COO--, --OCO--, --(CH₂)_(a) OCO--, --(CH₂)_(a) COO-- (ais an integer of 1 to 3), --O--, --SO₂ --, --CO--, --CON)T¹)--, --SO₂N(T¹)--, --CONHCOO--, --CONHCONH-- or --C₆ H₅ -- (T¹ has the samemeaning as defined in formula (II)), R₄ represents a hydrogen atom or ahydrocarbon group and b⁵ and b⁶ each has independently the same meaningas b¹ or b².
 14. The electrophotographic material for color proofing ofclaim 1, wherein said organic group has a molecular weight of not morethan 1,000.
 15. The process of claim 13, wherein said organic group hasa molecular weight of not more than 1,000.
 16. The process of claim 13,wherein said exposure is conducted based on digital information using alaser beam.
 17. The process of claim 13, wherein said photoconductivelayer further contains a photosetting agent or a thermosetting agent orboth.